Bipyridyl compound

ABSTRACT

There are provided a compound capable of being a novel ligand allowing regioselective borylation to be performed in the aromatic borylation reaction, and a catalyst using the same compound. There is provided a bipyridyl compound represented by a general formula (1): (wherein A represents a single bond, a vinylene group or an ethynylene group; 
     X represents an oxygen atom or a sulfur atom; 
     n pieces of R 1  may be the same or different, and R 1  represents a hydrogen atom, a halogen atom, an optionally substituted hydrocarbon group, an optionally substituted alkoxy group, an optionally substituted aryloxy group, an optionally substituted amino group, a cyano group, a nitro group, or an alkoxycarbonyl group, or two adjacent R 1  may form a saturated or unsaturated ring structure optionally containing a hetero atom together with the carbon atoms bonded to the two R 1 ; 
     R 2  represents a hydrogen atom, an optionally substituted hydrocarbon group, an optionally substituted alkoxy group, or an optionally substituted aryloxy group; and 
     n represents a number of  1  to  4 ).

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. application Ser. No.15/114,347 filed Jul. 26, 2016, which is pending and which is a NationalStage of PCT/JP2015/052450 filed Jan. 29, 2015 and claims the benefit ofJP 2014-015211 filed Jan. 30, 2014.

FIELD OF THE INVENTION

The present invention relates to a bipyridyl compound useful as a ligandof a metal catalyst and a catalyst including the same bipyridyl compoundas a ligand.

BACKGROUND OF THE INVENTION

The Suzuki-Miyaura reaction performing a cross coupling between anorganic halogen compound and an organic boron compound is an importantmethod for carbon-carbon bond formation reaction and is widely applied.The organic boron compound used in this reaction is stable against wateror air, and the product of the reaction is a boric acid salt to bethereby low in toxicity and has an advantage of being easily separablefrom the target product by washing with water.

For the purpose of synthesizing a wide range of compounds by using theSuzuki-Miyaura reaction, it is important to produce compounds eachhaving a boron atom bonded to a specific position in an aromaticcompound. In this connection, catalysts such as rhodium catalysts,iridium catalysts and rhenium catalysts are known as the catalysts forthe aromatic borylation reactions allowing boron atoms to be bonded toaromatic compounds. In these catalysts, bipyridyl compounds,ethylenediamine compounds, phenanthroline compounds, cyclopentadienylcompounds and the like are used as ligands (Non Patent Literature 1 toNon Patent Literature 9).

CITATION LIST Non Patent Literature

-   [Non Patent Literature 1]

J. Am. Chem. Soc. 1999, 121, 7696

-   [Non Patent Literature 2]

Science 2002, 295, 305

-   [Non Patent Literature 3]

J. Am. Chem. Soc. 2000, 122, 12868

-   [Non Patent Literature 4]

Org. Lett. 2001, 3, 2831

-   [Non Patent Literature 5]

Adv. Synth. Catal. 2003, 345, 1103

-   [Non Patent Literature 6]

J. Am. Chem. Soc. 2002, 124, 390

-   [Non Patent Literature 7]

Tetrahedron Lett. 2002, 43, 5649

-   [Non Patent Literature 8]

Angew. Chem. Int. Ed. 2002, 41, 3056

-   [Non Patent Literature 9]

J. Organomet. Chem. 2003, 680, 3

SUMMARY OF THE INVENTION Problem to be Solved by the Invention

However, there has been a problem such that when an aromatic borylationreaction is performed by using an iridium catalyst including a hithertoreported bipyridyl compound as a ligand, the control of the substitutionposition of a boron in an aromatic compound is difficult, and aselective borylation at an intended position is not achievable.

Accordingly, the technical problem of the present invention is toprovide a compound capable of being a novel ligand allowingregioselective borylation to be performed in the aromatic borylationreaction, and a catalyst using the same compound.

Solution to Problem

Thus, the present inventors made various studies on the ligand enablingregioselective borylation in the aromatic borylation reaction, andconsequently succeeded in the synthesis of a novel compound having abipyridine skeleton and a benzeneureido skeleton. Moreover, when anaromatic borylation reaction was performed by using a catalyst havingthe aforementioned compound as a ligand, the borylation reactionproceeded selectively at the meta position of the aromatic compound, andthus, the present inventors found that the aforementioned catalyst isuseful as a meta-selective borylation catalyst, and consequentlyaccomplished the present invention.

Specifically, the present invention provide the following [1] to [6].

-   [1] A bipyridyl compound represented by a general formula (1):

(wherein A represents a single bond, a vinylene group (—CH═CH—) or anethynylene group (—C≡C—);

X represents an oxygen atom or a sulfur atom;

n pieces of R¹ may be the same or different, and R¹ represents ahydrogen atom, a halogen atom, an optionally substituted hydrocarbongroup, an optionally substituted alkoxy group, an optionally substitutedaryloxy group, an optionally substituted amino group, a cyano group, anitro group, or an alkoxycarbonyl group, or two adjacent R¹ may form asaturated or unsaturated ring structure optionally containing a heteroatom together with the carbon atoms bonded to the two R¹;

R² represents a hydrogen atom, an optionally substituted hydrocarbongroup, an optionally substituted alkoxy group, or an optionallysubstituted aryloxy group; and

n represents a number of 1 to 4).

-   [2] The bipyridyl compound according to [1], wherein A is a single    bond.-   [3] The bipyridyl compound according to [1] or [2], wherein R¹ is a    hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon    atoms, an alkenyl group having 2 to 10 carbon atoms, a cycloalkyl    group having 3 to 7 carbon atoms, an aryl group having 6 to 10    carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an    alkoxy group having 1 to 10 carbon atoms, a C₁₋₆ alkylamino group, a    di (C₁₋₆ alkyl)amino group or a C₁₋₁₀ alkoxycarbonyl group.-   [4] The bipyridyl compound according to any one of [1] to [3],    wherein R² is a hydrogen atom, an optionally substituted alkyl group    having 1 to 10 carbon atoms, an optionally substituted alkenyl group    having 2 to 10 carbon atoms, an optionally substituted cycloalkyl    group having 3 to 7 carbon atoms, an optionally substituted aryl    group having 6 to 10 carbon atoms, an optionally substituted alkoxy    group having 1 to 10 carbon atoms or an optionally substituted    aryloxy group having 6 to 10 carbon atoms.-   [5] An aromatic borylation catalyst including the bipyridyl compound    according to any one of [1] to [4] as a ligand.-   [6] The catalyst according to [5], wherein the bipyridyl compound    according to any one of [1] to [4] is coordinated to iridium.

Effects of the Invention

The catalyst including the compound (1) of the present invention as aligand is useful as a catalyst to selectively introduce a boron atominto the meta position of an aromatic compound. Accordingly, the use ofthe catalyst including the compound (1) of the present invention as aligand enables the production of various regioselective aromatic boroncompounds usable in the coupling reaction such as the Suzuki-Miyaurareaction.

EMBODIMENTS TO CARRY OUT THE INVENTION

The bipyridyl compound of the general formula (1) is characterized byhaving both of a bipyridine skeleton and a benzeneureido skeleton.

In the general formula (1), A represents a single bond, a vinylene groupor an ethynylene group. Among these, a single bond or an ethynylenegroup are preferable, and a single bond is more preferable.

The bonding position of A in the benzene ring may be any of the orthoposition, meta position and para position in relation to the ureidogroup, and is more preferably the ortho position.

X represents an oxygen atom or a sulfur atom. Of these, an oxygen atomis preferable.

The n pieces of R¹ may be the same or different, and R¹ represents ahydrogen atom, a halogen atom, an optionally substituted hydrocarbongroup, an optionally substituted alkoxy group, an optionally substitutedaryloxy group, an optionally substituted amino group, a cyano group, anitro group, or an alkoxycarbonyl group, or two adjacent R¹ may form asaturated or unsaturated ring structure optionally containing a heteroatom together with the carbon atoms bonded to the two R¹ .

Examples of the halogen atom include a fluorine atom, a bromine atom, achlorine atom and an iodine atom.

As a hydrocarbon group, a hydrocarbon group having 1 to 16 carbon atomsis preferable, an alkyl group having 1 to 16 carbon atoms, an alkenylgroup having 2 to 16 carbon atoms, a cycloalkyl group having 3 to 16carbon atoms, an aryl group having 6 to 14 carbon atoms and an arylalkylgroup having 7 to 16 carbon atoms are more preferable, and an alkylgroup having 1 to 16 carbon atoms, an alkenyl group having 2 to 16carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms, an arylgroup having 6 to 10 carbon atoms and an arylalkyl group having 7 to 16carbon atoms are furthermore preferable.

Examples of the alkyl group having 1 to 16 carbon atoms include: linearor branched alkyl groups such as a methyl group, an ethyl group, ann-propyl group, an isopropyl group, an n-butyl group, an isobutyl group,a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentylgroup, an n-hexyl group, an n-octyl group and an n-decyl group. Examplesof the alkenyl group having 2 to 16 carbon atoms include: a vinyl group,an allyl group, a propenyl group, a butenyl group and a hexenyl group.Examples of the cycloalkyl group having 3 to 7 carbon atoms include: acyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexylgroup and a cycloheptyl group. Examples of the aryl group having 6 to 10carbon atoms include a phenyl group and a naphthyl group. Examples ofthe arylalkyl group having 7 to 16 carbon atoms include a phenyl-C₁₋₆alkyl group and a naphthyl-C₁₋₆ alkyl group.

As the alkoxy group, an alkoxy group having 1 to 16 carbon atoms ispreferable and an alkoxy group having 1 to 6 carbon atoms is morepreferable. Specific examples of the alkoxy group include a methoxygroup, an ethoxy group, an n-propyloxy group and an isopropyloxy group.Examples of the aryloxy group include a C₆₋₁₀ aryloxy group, and as thearyloxy group, a phenoxy group, a naphthyloxy group and the like aremore preferable.

Examples of the alkoxycarbonyl group include a C₁₋₆ alkoxycarbonylgroup, and specific examples of the alkoxycarbonyl group include amethoxycarbonyl group and an ethoxycarbonyl group.

Here, examples of the group capable of being substituted in thehydrocarbon group represented by R¹ include: 1 to 3 halogen atoms, acyano group, a nitro group, a halogeno C₁₋₆ alkyl group and a C₁₋₆alkoxy group. Examples of the group capable of being substituted in thealkoxy group and the aryloxy group include 1 to 3 halogen atoms, a cyanogroup, a nitro group, a halogeno C₁₋₆ alkyl group and a C₁₋₆ alkoxygroup. Examples of the group capable of being substituted in the aminogroup include a C₁₋₆ alkyl group and a halogeno C₁₋₆ alkyl group.

Here, n represents a number of 1 to 4, and is preferably a number of 1or 2.

The substitution position of R¹ is not particularly limited, but ispreferably a position not disturbing the coordination bonding of thenitrogen atom of the pyridine ring to a metal atom, namely, a positiondistant from the nitrogen atom, preferably a position at the metaposition or the para position relative to the nitrogen atom, andparticularly preferably the para position.

R² represents a hydrogen atom, an optionally substituted hydrocarbongroup, an optionally substituted alkoxy group, or an optionallysubstituted aryloxy group.

As the hydrocarbon group, a hydrocarbon group having 1 to 16 carbonatoms is preferable, an alkyl group having 1 to 16 carbon atoms, analkenyl group having 2 to 16 carbon atoms, a cycloalkyl group having 3to 16 carbon atoms, an aryl group having 6 to 14 carbon atoms and anarylalkyl group having 7 to 16 carbon atoms are more preferable, and analkyl group having 1 to 16 carbon atoms, an alkenyl group having 2 to 16carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms, an arylgroup having 6 to 10 carbon atoms and an arylalkyl group having 7 to 16carbon atoms are furthermore preferable.

Examples of the alkyl group having 1 to 16 carbon atoms include linearor branched alkyl groups such as a methyl group, an ethyl group, ann-propyl group, an isopropyl group, an n-butyl group, an isobutyl group,a sec-butyl group, a tent-butyl group, an n-pentyl group, an isopentylgroup, an n-hexyl group, an n-octyl group and an n-decyl group. Examplesof the alkenyl group having 2 to 16 carbon atoms include: a vinyl group,an allyl group, a propenyl group, a butenyl group and a hexenyl group.Examples of the cycloalkyl group having 3 to 7 carbon atoms include: acyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexylgroup and cycloheptyl group. Examples of the aryl group having 6 to 10carbon atoms include: a phenyl group and a naphthyl group. Examples ofthe arylalkyl group having 7 to 16 carbon atoms include a phenyl C₁₋₆alkyl group and a naphthyl C₁₋₆ alkyl group.

As the alkoxy group, an alkoxy group having 1 to 16 carbon atoms ispreferable, and an alkoxy group having 1 to 6 carbon atoms is morepreferable. Specific examples of the alkoxy group include: a methoxygroup, an ethoxy group, an n-propyloxy group and an isopropyloxy group.Examples of the aryloxy group include a C₆₋₁₀ aryloxy group, and aphenoxy group, a naphthyloxy group and the like are more preferable.

Examples of the group capable of being substituted in the hydrocarbongroup represented by R² include: 1 to 3 halogen atoms, a cyano group, anitro group, a halogeno C₁₋₆ alkyl group and a C₁₋₆ alkoxy group.Examples of the group capable of being substituted in an alkoxy groupand an aryloxy group include: 1 to 3 halogen atoms, a cyano group, anitro group, a halogeno C₁₋₆ alkyl group and a C₁₋₆ alkoxy group.

As R¹, a hydrogen atom, a halogen atom, an alkyl group having 1 to 10carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a cycloalkylgroup having 3 to 7 carbon atoms, an aryl group having 6 to 10 carbonatoms, an alkoxy group having 1 to 10 carbon atoms, an aryloxy grouphaving 6 to 10 carbon atoms, a C₁₋₆ alkylamino group, a di(C₁₋₆alkyl)amino group, a cyano group and a C₁₋₁₀ alkoxycarbonyl group aremore preferable.

As R², a hydrogen atom, an optionally substituted alkyl group having 1to 10 carbon atoms, an optionally substituted alkenyl group having 2 to10 carbon atoms, an optionally substituted cycloalkyl group having 3 to7 carbon atoms, an optionally substituted aryl group having 6 to 10carbon atoms, an optionally substituted alkoxy group having 1 to 10carbon atoms and an optionally substituted aryloxy group having 6 to 10carbon atoms are preferable.

Particularly preferable as R² are the C₁₋₁₀ alkyl group optionallysubstituted with the substituent (such as a halogen atom or a C₁₋₆alkoxy group), the C₃₋₇ cycloalkyl group optionally substituted with thesubstituent (such as a C₁₋₆ alkyl group, a halogeno C₁₋₆ alkyl group ora C₁₋₆ alkoxy group), and the phenyl group optionally substituted withthe substituent (such as a C₁₋₆ alkyl group, a halogeno C₁₋₆ alkyl groupor a C₁₋₆ alkoxy group).

The bipyridyl compound (1) can be produced according to, for example,the following reaction formula.

(wherein X¹ represents a halogen atom, X² represents a halogen atom, avinylene group or an ethynylene group, and R¹, A, X, R² and n are thesame as described above).

(First Step)

The first step is a step of obtaining a compound (4) by coupling abipyridine compound (2) and an aniline compound (3) with each other.

In the case where in the compound (3), X² is a halogen atom, preferableis the Suzuki-Miyaura coupling in which after the borylation of thecompound (3), the compound(3) is coupled with the compound (2). Theborylation reaction of the compound (3) can be performed by allowing aboron compound such as pinacolborane to react with the compound (3) inthe presence of palladium-phosphine and a base. The subsequent couplingreaction can be performed by adding a base such as barium hydroxide.

As the boron compound, pinacolborane, bis(pinacolato)diborane and thelike are used. As palladium-phosphine, for example,bis(diphenylphosphino)alkanes (such as DPPM, DPPE and DPPP),bis(diphosphino)ferrocene (DPPF), bis(diphenylphosphino)binaphthyl(BINAP) and xantphos are used. As the base, tertiary amines such astriethylamine are used.

Examples of the base used in the subsequent coupling reaction include:barium hydroxide, sodium carbonate, potassium carbonate and sodiumhydrogen carbonate.

The coupling reaction can be performed in an inert solvent such asdioxane at 50 to 100° C. for 2 to 12 hours.

In the case where in the compound (3), X² is an ethynylene group, thecoupling reaction is preferably performed by the Sonogashira couplingusing a palladium catalyst, a copper catalyst and a base.

Examples of the palladium catalyst include:tetrakis(triphenylphosphine)palladium(0) anddichlorobis(triphenylphosphine)palladium(II). As the copper catalyst,copper halides such as copper iodide are preferable. As the base,tertiary amines such as triethylamine are preferable.

The coupling reaction can be performed in an amine at 30 to 100° C. for1 to 10 hours.

(Second Step)

The second step is a step of obtaining the bipyridyl compound (1) byallowing an isocyanate (5) or a thioisocyanate (5) to react with thecompound (4).

This reaction can be performed by allowing an isocyanate (5) or athioisocyanate (5) to react with the compound (4), in an inert solventsuch as dichloromethane, at a temperature from room temperature to 100°C., for 1 to 10 hours.

The bipyridyl compound (1) thus obtained is useful as a ligand of anaromatic borylation catalyst for borylation of an aromatic compound.More specifically, a metal catalyst including the bipyridyl compound (1)as a ligand is useful as a catalyst for selective borylation of the metaposition of an aromatic compound, and hence the bipyridyl compound (1)is useful as a ligand of the aromatic borylation catalyst.

The aromatic borylation catalyst of the present invention is atransition metal catalyst in which the two nitrogen atoms in thebipyridine skeleton are coordination bonded to the transition metal (M).Examples of such a transition metal include: iridium (Ir), rhenium (Re),rhodium (Rh), palladium (Pd) and ruthenium (Ru); among these, iridium ismore preferable.

In the aromatic borylation catalyst, a compound other than the bipyridylcompound (1) can also be coordinated. Examples of such a ligand includecyclooctadiene (cod).

Such an aromatic borylation catalyst can be formed in a borylationreaction system by adding the bipyridyl compound (1) to, for example,M(OMe) (cod) or M(cod)(Cl).

The aromatic borylation reaction using the aromatic borylation catalystis described.

An aromatic compound and a boron compound such as pinacolborane orbis(pinacolato)diboron are allowed to react with each other in thepresence of the catalyst of the present invention, and thus a boron atomis introduced into the aromatic compound. In this case, the use of amonosubstituted aromatic compound as a raw material results in aselective introduction of a boron atom into the meta position of themonosubstituted aromatic compound. This reaction can be performed byusing a boron compound in an amount 0.50 to 10 moles in relation to 1mole of the aromatic compound, in an inert solvent such as p-xylene,cyclohexane or dioxane, at room temperature to 100° C. for 1 to 24hours. The amount used of the catalyst can be 1.5 molt in relation to 1mole of the aromatic compound. Here, examples of the aromatic compoundinclude an aromatic hydrocarbon having 6 to 50 carbon atoms and anaromatic heterocyclic compound having 5 to 45 carbon atoms. Examples ofthe substituted aromatic compound to be a substrate of the borylationreaction include: compounds having 1 to 2 substituents in these aromatichydrocarbons or these aromatic heterocyclic compounds. The substituentsin such mono- or disubstituted aromatic compounds are not particularlylimited; examples of the substituents include: a halogen atom, an alkylgroup, a cyclic alkyl group, a hydroxyl group, an alkoxy group, an aminogroup, an alkylamino group, a dialkylamino group, an acyl group, acarboxyl group, a carbamoyl group, an N-substituted carbamoyl group, aphosphate group, a phosphine group, a carboxyalkyl group, analkoxycarbonylalkyl group, a phosphinediamide group, an aromatichydrocarbon group and an aromatic heterocyclic group.

The aromatic boron compound thus obtained are usable as the rawmaterials for the coupling reaction such as the Suzuki-Miyaura coupling.

EXAMPLES

Next, the present invention is described in detail with reference toExamples, but the present invention is not limited by these Examples atall.

Example 1 (1) 2-([2,2′-Bipyridin]-5-yl)aniline

2-Bromoaniline (0.566 mL, 5.00 mmol, 1 equiv) was dissolved in 10 mL ofdioxane 10 mL, and to the resulting solution, triethylamine (2.80 mL,20.0 mmol, 4 equiv), PdCl₂ (dppf) (183 mg, 0.250 mmol, 5 mol %) andpinacolborane (2.2 mL, 15.0 mmol, 3 equiv) were added and stirred at100° C. for 4 hours. The reaction solution was cooled to roomtemperature, 2.2 mL of water, Ba(OH)₂.8H₂O (4.73 g, 15.0 mmol, 3 equiv)and 5′-bromo-2,2′-bipyridine (1.08 g, 4.60 mmol, 0.92 equiv) were addedto the reaction solution, and then further stirred at 100° C. for 4hours. The reaction solution was cooled to room temperature, thenfiltered with Celite, and washed with 120 mL of ethyl acetate. Thefiltrate was subjected to separatory washing with 120 mL of water, driedwith anhydrous sodium sulfate, and then filtered; the solvent wasremoved under reduced pressure to yield a crude product. By using asilica gel pretreated with a 20% triethylamine-hexane solution (200 mL),the crude product was subjected to a column purification (hexane/ethylacetate=3/1). Thus, 672 mg (yield: 59%) of a white solid was obtained.

-   59% yield; white solid; R_(f)=0.50 (hexane/ethyl acetate=1/1); ¹H    NMR (400 MHz, CDCl₃) δ 3.77 (s, 2H), 6.81 (d, J=7.8 Hz, 1H), 6.88    (d, J=7.5 Hz, 1H), 7.17 (d, J=7.5 Hz, 1H), 7.22 (d, J=7.8 Hz, 1H),    7.33 (dd, J=7.8, 5.2 Hz, 1H), 7.84 (dd, J=7.8, 7.8 Hz, 1H), 7.96 (d,    J=8.2 Hz, 1H), 8.43 (d, J=7.8 Hz, 1H), 8.47 (d, J=8.2 Hz, 1H), 8.71    (d, J=5.2 Hz, 1H), 8.80 (s, 1H); ¹³C NMR (100 MHz, CDCl₃) δ 116.0,    119.0, 121.0, 121.1, 123.6, 123.8, 129.5, 130.6, 135.3, 137.0,    137.5, 143.9, 149.3, 149.5, 154.9, 156.0; IR (KBr, ν/cm⁻¹) 3346,    3219, 1459, 1357, 1240, 1094, 994, 858, 751, 644; HRMS (ESI⁺) Calcd    for C₁₆H₁₃N₃Na ([M+Na]⁺) 270.1002, Found 270.1007.

(2) 1-(2-([2,2′-Bipyridin]-5-yl)phenyl)-3-cyclohexylurea

2-([2,2′-Bipyridin]-5-yl)aniline (371 mg, 1.5 mmol, 1.0 equiv),isocyanatecyclohexane (0.29 mL, 2.3 mmol, 1.5 equiv) were dissolved in5.0 mL of dichloromethane, and stirred at room temperature for 24 hours.The solvent was removed under reduced pressure from the reactionsolution to yield a crude product. By recrystallization(hexane/dichloromethane), 281 mg (yield: 50%) of a target product wasobtained.

-   50% yield; white solid; R_(f)=0.53 (hexane/ethyl acetate=1/2); ¹H    NMR (400 MHz, CDCl₃) δ 0.94-1.10 (m, 3H), 1.27-1.34 (m, 3H),    1.52-1.67 (m, 2H), 1.86-1.89 (m, 2H), 3.51-3.59 (m, 1H), 4.86-4.97    (m, 1H), 6.26-6.35 (m, 1H), 7.21 (dd, J=7.2, 6.3 Hz, 1H), 7.30 (d,    J=6.3 Hz, 1H), 7.35 (dd, J=7.2, 7.2 Hz, 1H), 7.42 (d, J=7.2 Hz, 1H),    7.84-7.87 (m, 2H), 7.92 (d, J=8.6 Hz, 1H), 8.39 (d, J=8.0 Hz, 1H),    8.44 (d, J=8.6 Hz, 1H), 8.69-8.71 (m, 2H);

¹³C NMR (125 MHz, CDCl₃) δ 25.0, 25.6, 33.7, 49.2, 121.1, 121.3, 122.5,123.8, 124.1, 129.0, 129.6, 130.4, 134.8, 136.6, 137.2, 137.9, 149.4,149.5, 154.8, 155.1, 155.5; IR (KBr, ν/cm⁻¹) 3245, 3219, 1458, 1367,1240, 1094, 994, 858, 751, 644; HRMS (ESI⁺)Calcd for C₂₃H₂₄N₄NaO([M+Na]⁺) 395.1842, Found 395.1850.

Examples 2 to 8

The following compounds were synthesized in the same manner as Example1.

Example 2 1-(2-([2,2′-Bipyridin]-5-yl)phenyl)-3-hexylurea

-   62% yield; white solid; R_(f)=0.32 (hexane/ethyl acetate=1/1); ¹H    NMR (500 MHz, CDCl₃) δ 0.79 (t, J=6.9 Hz, 3H), 1.16-1.22 (m, 6H),    1.33-1.38 (m, 2H), 3.14 (td, J=7.2, 7.2 Hz, 2H), 5.48 (brs, 1H),    6,70 (s, 1H), 7.12-7.20 (m, 2H), 7.32 (dd, J=6.3, 4.6, 1.2 Hz, 1H),    7.39 (ddd, J=6.3, 4.8, 1.1 Hz, 1H), 7.69 (ddd, J=8.5, 7.6, 2.2 Hz,    1H), 7.81 (ddd, J=7.7, 7.6, 1.6 Hz, 1H), 8.06 (d, J=8.1 Hz, 1H),    8.15 (d, J=8.5 Hz, 1H), 8.19 (d, J=8.1 Hz, 1H), 8.56 (d, J=2.2 Hz,    1H), 8.64 (dd, J=4.0, 1.1 Hz, 1H); ¹³C NMR (125 MHz, CDCl₃) δ 14.0,    22.5, 26.6, 30.0, 31.5, 40.2, 120.9, 121.1, 122.3, 123.2, 124.0,    128.4, 129.4, 130.1, 135.1, 136.9, 137.1, 137.1, 149.1, 149.4,    154.3, 155.2, 156.1; IR (KBr, ν/cm⁻¹) 3292, 2922, 2855, 1626, 1457,    1371, 1266, 1090, 856, 649; HRMS (ESI⁺) Calcd for C₂₃H₂₆N₄NaO    ([M+Na]⁺) 397.1999, Found 397.1997.

Example 3 1-(2-([2,2T-Bipyridin]-5-yl)phenyl)-3-(4-methoxyphenyl)urea

-   6.5% yield; white solid; R_(f)=0.50 (hexane/ethyl acetate=1/2); ¹H    NMR (400 MHz, CDCl₃) δ 3.62 (s, 3H), 6.71 (d, J=8.6 Hz, 2H), 6.98    (d, J=8.6 Hz, 2H), 7.20-7.22 (m, 1H), 7.36-7.38 (m, 3H), 7.46-7.49    (m, 1H), 7.54 (s, 1H), 7.81 (dd, J=8.0, 2.0 Hz, 1H), 7.89 (ddd,    J=8.0, 7.7, 1.7 Hz, 1H), 7.94-7.96 (m, 1H), 8.44 (d, J=8.0 Hz, 1H),    8.46 (d, J=8.0 Hz, 1H), 8.63 (d, J=1.7 Hz, 1H), 8.73 (d, J=4.6 Hz,    1H); ¹³C NMR (125 MHz, DMSO-d₆) δ 55.6, 114.1, 120.4, 121.0, 124.7,    126.8, 127.8, 129.2, 130.2, 130.6, 132.0, 135.5, 135.7, 137.1,    137.6, 137.9, 149.3, 149.8, 154.2, 155.3, 157.2, 181.4; IR (KBr,    ν/cm⁻¹) 3278, 1636, 1509, 1458, 1370, 1244, 1111, 855, 756, 649;    HRMS (ESI⁺) Calcd for C₂₄H₂₀N₄NaO₂([M+Na]⁺) 419.1478, Found    419.1458.

Example 41-(2-([2,2′-Bipyridin]-5-yl)phenyl)-3-(4-trifluoromethylphenyl)urea

-   50% yield; pale yellow solid; R_(f)=0.63 (hexane/ethyl acetate=1/2);    ¹H NMR (400 MHz, CDCl₃) δ 7.10-7.16 (m, 2H), 7.35-7.53 (m, 7H), 7.64    (d, J=8.1 Hz, 1H), 7.84-7.85 (m, 2H), 8.22 (brs, 1H), 8.42 (d, J=8.3    Hz, 1H), 8.52 (d, J=1.3 Hz, 1H), 8.57 (d, J=3.1 Hz, 1H), 9.35 (brs,    1H); ¹³C NMR (125 MHz, CDCl₃) δ 118.1, 118.7, 121.1, 121.3, 123.2,    123.6 (q, J=33.6 Hz), 124.3 (q, J=271 Hz), 124.5, 126.1 (q, J=3.6    Hz), 127.2, 129.9, 130.3, 135.8, 136.9, 137.7, 138.6, 143.0, 149.5,    150.1, 153.2, 153.5, 154.3; ¹⁹F NMR (368 MHz, CDCl₃) δ −63.8 (s,    3F); IR (KBr, ν/cm⁻¹) 3331, 3058, 1716, 1654, 1449, 1329, 1165,    1014, 842, 759; HRMS (ESI⁺) Calcd for C₂₄H₁₇F₃N₄NaO ([M+Na]⁺)    457.1247, Found 457.1252.

Example 5 1-(2-([2,2′-Bipyridin]-5-yl)phenyl)-3-(4-butylphenyl)urea

276 yield; white solid; R_(f)=0.64 (hexane/ethyl acetate=1/2); ¹H NMR(400 MHz, CDCl₃) δ 0.85 (t, J=7.5 Hz, 3H), 1.20-1.28 (m, 2H), 1.38-1.46(m, 2H), 2.38 (t, J=7.7 Hz, 2H), 6.94 (d, J=1.9 Hz, 2H), 7.05-7.15 (m,4H), 7.34 (dd, J=7.2, 4.9 Hz, 1H), 7.41 (ddd, J=7.7, 7.7, 1.7 Hz, 1H),7.59 (d, J=8.0 Hz, 1H), 7.82 (dd, J=7.2, 7.2 Hz, 1H), 8.01-8.03 (m, 1H),8.15-8.16 (m, 1H), 8.30 (d, J=8.6 Hz, 1H), 8.52 (s, 1H), 8.65 (d, J=4.6Hz, 1H);

¹³C NMR (125 MHz, CDCl₃) δ 14.0, 22.4, 33.7, 35.0, 120.6, 121.0, 121.3,121.4, 123.2, 124.2, 127.8, 129.0, 129.6, 130.2, 135.1, 136.2, 136.8,137.3, 138.1, 138.3, 149.4, 149.7, 153.6, 154.4, 155.0; IR (KBr, ν/cm⁻¹)3293, 1637, 1546, 1509, 1458, 1372, 1246, 1122, 799, 757; HRMS (ESI⁺)Calcd for C₂₇H₂₆N₄NaO ([M+Na]⁺) 445.1999, Found 445.1989.

Example 6 1-(2-([2,2′-Bipyridin]-5-yl)phenyl)-3-(2,6-dimethylphenyl)urea

-   58% yield; white solid; R_(f)=0.30 (hexane/ethyl acetate=1/1); ¹H    NMR (400 MHz, CDCl₃) δ 2.15 (s, 6H), 5.73 (s, 1H), 6.19 (s, 1H),    6.78-6.80 (m, 1H), 6.84 (d, J=6.7 Hz, 2H), 7.13-7.18 (m, 2H),    7.36-7.44 (m, 2H), 7.48 (d, J=7.6 Hz, 1H), 7.89 (ddd, J=7.6, 7.6,    1.8 Hz, 1H), 8.23 (d, J=8.1 Hz, 1H), 8.29 (d, J=8.5 Hz, 1H), 8.39    (s, 1H), 8.43 (d, J=8.1 Hz, 1H), 8.75 (d, J=4.9 Hz, 1H);

¹³C NMR (125 MHz, CDCl₃) δ 18.3, 120.9, 121.1, 124.1, 128.4, 128.5,129.0, 129.6, 130.0, 132.8, 133.8, 136.1, 137.0, 137.1, 137.3, 149.1,149.5, 154.1, 155.3, 155.6, 155.7, 157.0; IR (KBr, ν/cm⁻¹) 3265, 1632,1550, 1457, 1371, 1240, 1002, 855, 797, 717; HRMS Calcd for C₂₅H₂₂N₄NaO([M+Na]⁺) 417.1686, Found 417.1679.

Example 7 1-(2-([2,2′-Bipyridin]-5-yl)phenyl)-3-cyclohexylthiourea

-   51% yield; white solid; R_(f)=0.36 (hexane/ethyl acetate=1/1); ¹H    NMR (400 MHz, CDCl₃) δ 0.96-1.12 (m, 3H), 1.24-1.37 (m, 2H),    1.55-1.63 (m, 4H), 1.90-1.93 (m, 2H), 4.14 (s, 1H), 5.71 (s, 1H),    7.30-7.34 (m, 2H), 7.41-7.54 (m, 3H), 7.82 (d, J=8.1 Hz, 1H), 7.85    (ddd, J=8.1, 8.1, 2.2 Hz, 1H), 8.40 (d, J=8.1 Hz, 1H), 8.47 (d,    J=9.0 Hz, 1H), 8.68-8.73 (m, 2H); ¹³C NMR (100 MHz, CDCl₃) δ 24.8,    25.5, 32.7, 54.1, 121.1, 121.4, 124.0, 127.9 (2C), 128.6, 130.0,    131.6, 133.6, 135.3, 137.0 (2C), 148.9, 149.4, 155.7, 155.8, 179.5;    IR (KBr, ν/cm⁻¹) 3293, 2931, 2857, 1637, 1458, 1373, 1229, 1001,    841, 656; HRMS (ESI⁺) Calcd for C₂₃H₂₄N₄NaS ([M+Na]⁺) 411.1619,    Found 411.1611.

Example 8 (1) 2-([2,2′-Bipyridin]-5-ylethynyl)aniline

-   A triethylamine (1.3 mL) solution of PdCl₂(PPh₃)₂ (1.8 mg, 2.5 μmol,    0.5 mol %), CuI (1.0 mg, 5.0 μmol, 1.0 mol %) and    5-bromo-2,2′-bipyridine (118 mg, 0.50 mmol, 1 equiv) was stirred for    15 minutes at room temperature. To the resulting solution,    2-ethylaniline (93 μL, 0.6 mmol, 1.2 equiv) was added, and then    stirred at 70° C. for 3.5 hours. The temperature of the solution was    cooled to room temperature, then the solid substances were removed    by filtration with Celite, and the obtained filtrate was washed with    water (20 mL) and was subjected to extraction with diethyl ether    (3×20 mL). The crude product was isolated and purified by silica gel    column chromatography (hexane/ethyl acetate=3/1), and thus 106 mg    (yield: 78%) of a target product was obtained as a white solid.-   78% yield; white solid; R_(f)=0.15 (hexane/ethyl acetate=3/1); ¹H    NMR (400 MHz, CDCl₃) δ 4.32 (brs, 2H), 6.72-6.77 (m, 2H), 7.18 (dt,    J=7.6, 1.3 Hz, 1H), 7.34 (dd, J=7.6, 4.9 Hz, 1H), 7.40 (dd, J=8.1,    1.8 Hz, 1H), 7.84 (dd, J=7.6, 7.6 Hz, 1H), 7.93 (dd, J=8.1, 2.2 Hz,    1H), 8.41-8.44 (m, 2H), 8.70 (d, J=4.0 Hz, 1H), 8.81 (dd, J=8.2, 1.8    Hz, 1H); ¹³C NMR (125 MHz, CDCl₃) δ 90.4, 91.8, 107.3, 114.6, 118.2,    120.5 (2C), 121.5, 124.0, 130.4, 132.5, 137.1, 139.2, 148.1, 149.4,    151.5, 154.9, 155.6; IR (KBr, ν/cm⁻¹) 3313, 2362, 2206, 1624, 1569,    1488, 1459, 1312, 1093, 739; HRMS (ESI⁺) Calcd for C₁₈H₁₃N₃Na    ([M+Na]⁺) 294.1007, Found 294.0999.

(2) 1-(2-([2,2T-Bipyridin]-5-ylethynyl)phenyl)-3-phenylurea

The target product was produced in the same manner as Example 1 (2).

-   46% yield; white solid; R_(f)=0.29 (ethyl acetate); ¹H NMR (500 MHz,    CDCl₃) δ 6.49 (brs, 1H), 7.04-7.10 (m, 3H), 7.29-7.30 (m, 1H),    7.34-7.41 (m, 4H), 7.47-7.49 (m, 2H), 7.58 (d, J=6.3 Hz, 1H), 7.86    (dd, J=5.8, 5.8 Hz, 1H), 8.30 (d, J=6.7 Hz, 1H), 8.37 (d, J=10.2 Hz,    1H), 8.44 (d, J=6.3 Hz, 1H), 8.56 (s, 1H), 8.72 (d, J=3.6 Hz, 1H);    ¹³C NMR (125 MHz, CDCl₃) δ 88.8, 92.7, 111.4, 119.4, 134.4, 120.4,    121.6, 122.8, 123.4, 124.3, 125.7, 127.7, 129.8, 130.5, 132.2,    137.2, 139.5, 139.9, 149.5, 151.7, 153.0, 155.3, 155.4; IR (KBr,    ν/cm⁻¹) 3299, 1644, 1576, 1552, 1458, 1296, 1091, 794, 743, 692;    HRMS (ESI⁺) Calcd for C₂₅H₁₈N₄NaO ([M+Na]⁺) 413.1378, Found    413.1388.

Example 9 (1) Meta-Selective Borylation of an Aromatic Compound With anIridium Catalyst

In a dried test tube, to a p-xylene (1.5 mL) solution ofN,N-dihexylbenzamide (72.4 mg, 0.250 mmol, 1.00 equiv), [Ir(OMe) (cod)]₂(1.2 mg, 1.9 μmol, 0.75 mol %),1-(2-([2,2′-bipyridin]-5-yl)phenyl)-3-cyclohexylurea (1.2 mg, 3.8 μmol,1.5 mol %) and bis(pinacolato)diboron (47.6 mg, 0.188 mmol, 0.750 equiv)were added and stirred at 25° C. for 24 hours. The solvent was removedunder reduced pressure, and then the products were isolated and preparedby recycling preparative HPLC.

The obtained compounds were as follows.

N,N-Dihexyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzamide

-   40% yield; colorless oil; ¹H NMR (500 M Hz, CDCl₃) δ 0.82 (t, J=6.9    Hz, 3H), 0.89-0.92 (m, 3H), 1.10-1.21 (m, 6H), 1.30-1.41 (m, 18H),    1.46-1.50 (m, 2H), 1.65-1.66 (m, 2H), 3.15 (t, J=6.9 Hz, 2H), 3.46    (t, J=7.2 Hz, 2H), 7.38 (dd, J=8.0, 7.2 Hz, 1H), 7.43 (ddd, J=8.0,    1.7, 1.7 Hz, 1H), 7.78 (s, 1H), 7.80 (ddd, J=7.2, 1.7, 1.7 Hz, 1H);    ¹³C NMR (100 MHz, CDCl₃) δ 14.1, 14.2, 22.6, 22.8, 25.0, 26.3, 26.9,    27.6, 28.8, 31.4, 31.8, 45.0, 49.2, 84.1, 127.8, 129.3, 132.7,    135.4, 136.8, 171.8; ¹¹B NMR (130 MHz, CDCl₃) δ 30.2; IR (neat,    ν/cm⁻¹) 2930, 2858, 1626, 1411, 1358, 1319, 1144, 861, 754, 666;    HRMS (ESI⁺) Calcd for C₂₅H₄₂BNNaO₃([M+Na]⁺) 438.3150, Found    438.3151.

N,N-Dihexyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzamide

-   3.3o yield; colorless oil; ¹H NMR (500MHz, CDCl₃) δ 0.82 (t, J=7.2    Hz, 3H), 0.89-0.92 (m, 3H), 1.06-1.11 (m, 4H), 1.18-1.25 (m, 2H),    1.35-1.36 (m, 18H), 1.46-1.47 (m, 2H), 1.63-1.66 (m, 2H), 3.13 (t,    J=6.9 Hz, 2H), 3.46 (t, J=7.2 Hz, 2H), 7.32 (d, J=8.3 Hz, 2H), 7.81    (d, J=8.3 Hz, 2H); ¹³C NMR (125 MHz, CDCl₃) δ 14.0, 14.1, 22.5,    22.7, 25.0, 26.3, 26.8, 27.6, 28.7, 31.4, 31.7, 44.8, 49.0, 84.1,    125.7, 134.8, 140.1, 171.6; ¹¹B NMR (130 MHz, CDCl₃) δ 29.9; IR    (neat, ν/cm⁻¹) 2929, 1636, 1511, 1396, 1360, 1322, 1144, 1108, 859,    659; HRMS (ESI⁺) Calcd for C₂₅H₄₂BNNaO₃ ([M+Na]⁺) 438.3150, Found    438.3170.

N,N-Dihexyl-3,5-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzamide

-   3.0% yield; colorless oil; ¹H NMR (500 MHz, CDCl₃) δ 0.81 (t, J=7.2    Hz, 3H), 0.90-0.93 (m, 3H), 1.10-1.27 (m, 10H), 1.31-1.35 (m, 28H),    1.62-1.66 (m, 2H), 3.12 (t, J=6.9 Hz, 2H), 3.44 (t, J=7.2 Hz, 2H),    7.88 (s 2H), 8.26 (s, 1H); ¹³C NMR (100 MHz, CDCl₃) δ 14.1, 14.2,    22.5, 22.8, 25.0, 26.3, 27.0, 27.7, 28.9, 31.4, 31.8, 45.0, 49.3,    84.0, 135.5, 136.3, 141.7, 171.7; ¹¹B NMR (130 MHz, CDCl₃) δ 32.9;    IR (neat, ν/cm⁻) 2929, 1628, 1329, 1265, 1142, 967, 889, 801, 755,    718; HRMS (ESI⁺) Calcd for C₃₁H₅₃B₂NNaO₅([M+Na]⁺) 564.4002, Found    564.4021.-   By using the ligand used in (1), the following compounds ((2) to    (27)) were obtained in the same manner as the method of (1).

(2)N,N-Dihexyl-2-methoxy-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzamideandN,N-dihexyl-2-methoxy-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzamide

-   63% yield [meta/para=7.5]; colorless oil; ¹¹B NMR (130 MHz, CDCl₃) δ    31.9; IR (neat, ν/cm⁻¹) 2930, 1627, 1410, 1355, 1140, 1027, 965,    851, 754, 683; HRMS (ESI⁺) Calcd for C₂₆H₄₄BNNaO₄([M+Na]⁺) 468.3256,    Found 468.3246.    N,N-Dihexyl-2-methoxy-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzamide:    ¹H NMR (400 MHz, CDCl₃) δ 0.80 (t, J=7.4 Hz, 3H), 0.91 (t, J=6.7 Hz,    3H), 1.06-1.08 (m, 4H), 1.16-1.50 (m, 22H), 1.62-1.64 (m, 2H),    3.01-3.04 (m, 2H), 3.48-3.49 (m, 2H), 3.82 (s, 3H), 6.87 (d, J=8.3    Hz, 1H), 7.63 (s, 1H), 7.76 (d, J=8.3 Hz, 1H); ¹³C NMR (125 MHz,    CDCl₃) δ 14.1, 14.2, 22.5, 22.8, 24.7, 26.3, 26.7, 27.6, 28.4, 31.4,    31.8, 44.4, 48.5, 55.4, 83.7, 110.1, 126.6, 134.4, 137.0, 157.8,    169.2.    N,N-Dihexyl-2-methoxy-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzamide:    ¹H NMR (400 MHz, CDCl₃) δ 0.80 (t, J=7.4 Hz, 3H), 0.91 (t, J=6.7 Hz,    3H), 1.06-1.08 (m, 4H), 1.18-1.50 (m, 20H), 1.62-1.64 (m, 4H),    3.01-3.04 (m, 2H), 3.48-3.49 (m, 2H), 3.85 (s, 3H), 7.17 (d, J=7.2    Hz, 1H), 7.29 (s, 1H), 7.41 (d, J=7.2 Hz, 1H); ¹³C NMR (125 MHz,    CDCl₃) δ 14.1, 14.2, 22.6, 22.8, 25.0, 26.3, 26.8, 27.5, 28.4, 31.4,    31.8, 44.3, 48.3, 55.6, 84.1, 116.4, 127.1, 127.4, 130.0, 154.6,    169.2.

(3)N,N-Dihexyl-2-methyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzamideandN,N-dihexyl-2-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzamide

-   39% yield [meta/para=15]; colorless oil; IR (neat, ν/cm⁻¹) 2929,    1634, 1466, 1357, 1145, 1105, 965, 862, 754, 686; HRMS (ESI⁺) Calcd    for C₂₆H₄₄BNNaO₃ ([M+Na]⁺) 452.3306, Found 452.3306.-   N,N-Dihexyl-2-methyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzamide:    ¹H NMR (500 MHz, CDCl₃) δ 0.82 (t, J=7.2 Hz, 3H), 0.91 (t, J=6.9 Hz,    3H), 1.07-1.11 (m, 4H), 1.14-1.21 (m, 2H), 1.25-1.39 (m, 18H),    1.41-1.47 (m, 2H), 1.62-1.70 (m, 2H), 2.29 (s, 3H), 3.01-3.05 (m,    2H), 3.39-3.56 (m, 2H), 7.19 (d, J=7.5 Hz, 1H), 7.59 (s, 1H), 7.67    (d, J=7.5 Hz, 1H); ¹³C NMR (125 MHz, CDCl₃) 8 14.1, 14.2, 19.4,    22.5, 22.8, 25.0, 26.3, 27.0, 27.7, 28.5, 31.3, 31.8, 44.6, 48.6,    83.9, 129.8, 132.3, 134.9, 136.8, 137.4, 171.3; ¹¹13 NMR (130 MHz,    CDCl₃) δ 30.5;-   N,N-Dihexyl-2-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzamide:    ¹H NMR (500 MHz, CDCl₃) δ 0.81 (t, J=7.2 Hz, 3H), 0.90 (t, J=6.0 Hz,    3H), 1.04-1.11 (m, 4H), 1.14-1.26 (m, 2H), 1.28-1.47 (m, 20H),    1.62-1.67 (m, 2H), 2.27 (s, 3H), 2.85-3.15 (m, 2H), 3.20-3.75 (m,    2H), 7.14 (d, J=7.8 Hz, 1H), 7.62 (d, J=7.8 Hz, 1H), 7.64 (s, 1H);    ¹³C NMR (125 MHz, CDCl₃) δ 14.1, 14.2, 18.9, 22.6, 22.8, 25.0, 26.4,    27.0, 27.6, 28.5, 31.4, 31.8, 44.4, 48.4, 84.1, 125.3, 132.2, 133.2,    136.7, 140.1, 171.2; ¹¹B NMR (130 MHz, CDCl₃) δ 31.3.

(4)2-Bromo-N,N-dihexyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzamideand2-bromo-N,N-dihexyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzamide

-   91% yield [meta/para=8.6]; colorless oil; ¹¹B NMR (130 MHz, CDCl₃) δ    30.0; IR (neat, ν/cm⁻¹) 2929, 1640, 1590, 1355, 1144, 1094, 964,    839, 754, 688; HRMS (ESI⁺) Calcd for C₂₅H₄₁BBrNNaO₃ ([M+Na]⁺)    516.2255, Found 516.2245.    2-Bromo-N,N-dihexyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzamide:    ¹H NMR (400 MHz, CDCl₃) δ 0.80 (t, J=7.2 Hz, 3H), 0.91 (t, J=6.7 Hz,    3H), 1.07-1.10 (m, 4H), 1.16-1.20 (m, 2H), 1.32-1.34 (m, 16H),    1.45-1.59 (m, 4H), 1.66-1.68 (m, 2H), 3.01-3.08 (m, 2H), 3.22-3.29    (m, 1H), 3.66-3.73 (m, 1H), 7.55 (d, J=7.9 Hz, 1H), 7.61 (dd, J=7.9,    1.4 Hz, 1H), 7.67 (d, J=1.4 Hz, 1H); ¹C NMR (125 MHz, CDCl₃) δ 14.0,    14.2, 22.4, 22.7, 24.8 (br), 26.2, 26.9, 27.3, 28.3, 31.3, 31.7,    44.6, 48.3, 84.2, 122.8, 132.1, 134.2, 135.9, 138.4, 168.9.-   2-Bromo-N,N-dihexyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzamide:    ¹H NMR (400 MHz, CDCl₃) δ 0.80 (t, J=7.2 Hz, 3H), 0.91 (t, J=6.7 Hz,    3H), 1.07-1.10 (m, 4H), 1.16-1.20 (m, 2H), 1.32-1.34 (m, 16H),    1.45-1.59 (m, 4H), 1.66-1.68 (brs, 2H), 3.01-3.08 (m, 2H), 3.22-3.29    (m, 1H), 3.66-3.73 (m, 1H), 7.23 (d, J=7.4 Hz, 1H), 7.73 (d, J=7.4    Hz, 1H), 7.98 (s, 1H); ¹³C NMR (125 MHz, CDCl₃) δ 14.0, 14.2, 22.5,    22.7, 24.9 (br), 26.3, 26.9, 27.2, 28.3, 31.2, 31.7, 44.7, 48.5,    84.4, 119.1, 127.3, 133.6, 138.7, 141.3, 168.8.

(5)2-Chloro-N,N-dihexyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzamideand2-chloro-N,N-dihexyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzamide

-   84% yield [meta/para=12]; pale yellow oil; HRMS (ESI⁺) Calcd for    C₂₅H₄₁BClNNaO₃ ([M+Na]⁺) 472.2760, Found 472.2764.    2-Chloro-N,N-dihexyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzamide:    ¹H NMR (400 MHz, CDCl₃) δ 0.80 (t, J=7.2 Hz, 3H), 0.91 (t, J=6.7 Hz,    3H), 1.08-1.19 (m, 6H), 1.25-1.61 (m, 20H), 1.63-1.69 (m, 2H),    2.98-3.12 (m, 2H), 3.28-3.34 (m, 1H), 3.64-3.70 (m, 1H), 7.36 (d,    J=8.5 Hz, 1H), 7.69 (s, 1H), 7.70 (d, J=8.5 Hz, 1H); ¹³C NMR (125    MHz, CDCl₃) δ 14.1, 14.2, 22.5, 22.8, 24.8, 26.3, 26.9, 27.4, 28.4,    31.3, 31.8, 44.7, 48.5, 84.3, 129.0, 133.5, 134.3, 136.0, 136.4,    168.2; ¹H NMR (130 MHz, CDCl₃) δ 32.1; IR (neat, ν/cm⁻¹) 2929, 2857,    1645, 1507, 1456, 1387, 1144, 1095, 963, 732.-   2-Chloro-N,N-dihexyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzamide:    ¹H NMR (400 MHz, CDCl₃) δ0.81 (t, J=7.2 Hz, 3H), 0.90 (t, J=6.5 Hz,    3H), 1.07-1.20 (m, 6H), 1.25-1.51 (m, 20H), 1.65-1.67 (m, 2H),    2.98-3.12 (m, 2H), 3.19-3.26 (m, 1H), 3.71-3.79 (m, 1H), 7.25 (d,    J=7.6 Hz, 1H), 7.69 (d, J=7.6 Hz, 1H), 7.80 (s, 1H); ¹³C NMR (125    MHz, CDCl₃) δ 14.1, 14.2, 22.5, 22.8, 25.0, 26.4, 26.9, 27.3, 28.4,    31.4, 31.8, 44.6, 48.5, 84.3, 127.4, 132.2, 133.1, 135.7, 139.3,    168.1; ¹H NMR (130 MHz, CDCl₃) 8 30.2; IR (neat, ν/cm⁻¹) 2929, 2857,    1644, 1498, 1456, 1355, 1143, 1096, 1047, 686.

(6)N,N-Dihexyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-(trifluoromethyl)benzamide

-   93% yield; colorless oil; ¹NMR (500 MHz, CDCl₃) δ 0.80 (t, J=7.2 Hz,    3H), 0.91 (t, J=6.7 Hz, 3H), 1.07-1.22 (m, 6H), 1.33-1.49 (m, 20H),    1.64-1.65 (m, 2H), 2.88-3.04 (m, 2H), 3.13-3.23 (m, 1H), 3.69-3.79    (m, 1H), 7.65 (d, J=7.9 Hz, 1H), 7.75 (s, 1H), 7.88 (d, J=7.9 Hz,    1H);

¹³C NMR (100 MHz, CDCl₃) δ 14.0, 14.1, 22.4, 22.7, 24.9, 26.2, 26.8,27.0, 28.0, 31.3, 31.7, 44.5, 48.8, 84.5, 123.8 (q, J=275 Hz), 125.6 (q,J=4.8 Hz), 127.1, 128.7 (q, J=31.2 Hz), 133.8, 134.9, 168.6; ¹⁹F NMR(368 MHz, CDCl₃) δ −62.0; ¹¹B NMR (130 MHz, CDCl₃) δ 30.5; IR (neat,ν/cm⁻¹) 2930, 2859, 1644, 1505, 1467, 1312, 1102, 1041, 844, 690; HRMS(ESI⁺) Calcd for C₂₆H₄₁BF₃NNaO₃([M+Na]⁺) 506.3024, Found 506.3018.

-   (7)    N,N-Dihexyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-(trifluoromethoxy)benzamide    and    N,N-dihexyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-(trifluoromethoxy)benzamide

-   92% yield [meta/para=6.8]; colorless oil; ¹⁹F NMR (368 MHz, CDCl₃) δ    −58.6; ¹¹B NMR (130 MHz, CDCl₃) δ 30.2; IR (neat, ν/cm⁻¹) 2931,    2859, 1644, 1468, 1359, 1255, 1003, 965, 850, 687; HRMS (ESI⁺) Calcd    for C₂₆H₄₁BF₃NNaO₄ ([M+Na]⁺) 522.2973, Found 522.2996.    N,N-Dihexyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-(trifluoromethoxy)benzamide:    ¹NMR (400 MHz, CDCl₃) δ 0.80 (t, J=7.2 Hz, 3H), 0.90 (t, J=6.7 Hz,    3H), 1.08-1.09 (m, 4H), 1.17-1.20 (m, 2H), 1.32-1.45 (m, 20H),    1.62-1.67 (m, 2H), 3.04 (t, J=7.6 Hz, 2H), 3.19-3.26 (m, 1H),    3.72-3.76 (m, 1H), 7.25 (d, J=8.3 Hz, 1H), 7.75 (s, 1H), 7.82 (d,    J=8.3 Hz, 1H); ¹³C NMR (100 MHz, CDCl₃) δ 13.9, 14.1, 22.4, 22.6,    24.9, 26.2, 26.7, 27.2, 28.3, 31.2, 31.7, 44.4, 48.4, 84.3, 118.6    (q, J=1.9 Hz), 123.8 (q, J=258 Hz), 129.8, 135.2, 136.7, 147.1 (q,    J=1.9 Hz), 166.8.-   N,N-Dihexyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-(trifluoromethoxy)benzamide:    ¹H NMR (400 MHz, CDCl₃) δ 0.80 (t, J=7.2 Hz, 3H), 0.90 (t, J=6.7 Hz,    3H), 1.08-1.09 (m, 4H), 1.17-1.20 (m, 2H), 1.32-1.45 (m, 20H),    1.62-1.67 (m, 2H), 3.04 (t, J=7.6 Hz, 2H), 3.19-3.26 (m, 1H),    3.72-3.76 (m, 1H), 7.33 (d, J=7.4 Hz, 1H), 7.67 (s, 1H), 7.73 (d,    J=7.4 Hz, 1H); ¹³C NMR (100 MHz, CDCl₃) 813.9, 14.1, 22.5, 22.6,    24.8, 26.2, 26.7, 27.2, 28.3, 31.3, 31.7, 44.4, 48.3, 84.4, 123.8    (q, J=258 Hz), 125.9, 127.9, 133.2, 133.3, 144.5 (q, J=1.9 Hz),    166.7.

(8) Methyl2-(dihexylcarbamoyl)-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzoate

-   96% yield; pale yellow oil; ¹H NMR (400 MHz, CDCl₃) δ 0.79 (t, J=7.2    Hz, 3H), 0.91 (t, J=7.0 Hz, 3H), 1.05-1.07 (m, 4H), 1.15-1.20 (m,    2H), 1.30-1.47 (m, 20H), 1.69-1.72 (m, 2H), 2.99 (t, J=7.8 Hz, 2H),    3.45-3.49 (m, 2H), 3.86 (s, 3H), 7.70 (d, J=1.0 Hz, 1H), 7.83 (dd,    J=8.0, 1.0 Hz, 1H), 7.99 (d, J=8.0 Hz, 1H); ¹³C NMR (100 MHz, CDCl₃)    δ 13.9, 14.1, 22.3, 22.7, 24.8, 26.2, 26.9, 27.1, 28.0, 31.2, 31.7,    44.8, 48.8, 52.2, 84.3, 129.1, 129.6, 133.4, 134.5, 138.3, 166.2,    170.6; ¹¹B NMR (130 MHz, CDCl₃) δ 29.6; IR (neat, ν/cm⁻¹) 2930,    2858, 1730, 1639, 1494, 1359, 1143, 964, 855, 795; HRMS (ESI⁺) Calcd    for C₂₇H₄₄BNNaO₅([M+Na]⁺) 496.3205, Found 496.3186.

(9)N,N-Dihexyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-[1,1′-biphenyl]-2-carboxamide

-   26% yield; colorless oil; ¹HNMR (400 MHz, CDCl₃) δ 0.79 (t, J=7.2    Hz, 3H), 0.88 (t, J=7.0 Hz, 3H), 0.92-1.01 (m, 4H), 1.05-1.28 (m,    10H), 1.34 (s, 12H), 1.62-1.66 (m, 2H), 2.48-2.54 (m, 1H), 2.80-2.98    (m, 2H), 3.54-3.61 (m, 1H), 7.30-7.41 (m, 4H), 7.48-7.50 (m, 2H),    7.82 (s, 1H), 7.85 (dd, J=7.9, 1.1 Hz, 1H); ¹³C NMR (100 MHz, CDCl₃)    δ 14.1, 14.2, 22.5, 22.7, 24.8, 25.1, 26.2, 26.9, 27.9, 31.3, 31.8,    44.4, 48.3, 84.0, 127.8, 128.4, 128.7, 128.9, 134.1, 135.2, 136.0,    140.0, 141.0, 171.1; ¹¹B NMR (130 MHz, CDCl₃) δ 31.8; IR (neat,    ν/cm⁻¹) 2928, 2857, 1629, 1466, 1387, 1318, 1144, 965, 700, 611;    HRMS (ESI⁺) Calcd for C₃₁H₄₆BNNaO₃([M+Na]⁺) 514.3463, Found    514.3452.

(10)2-Methyl-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-isoindolin-1-one,and2-methyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-isoindolin-1-one

-   39% yield [meta/para=3.3]; pale yellow solid; ¹¹B NMR (130 MHz,    CDCl₃) δ 30.8; IR (neat, ν/cm⁻¹) 2978, 2932, 1680, 1397, 1355, 1337,    1309, 1258, 1202, 1143, 1115, 967, 863, 849, 714, 655; HRMS (ESI⁺)    Calcd for C₁₅H₂₀BNNaO₃([M+Na]⁺) 296.1434, Found 296.1438.    2-Methyl-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2⁻yl)⁻isoindolin-1-one:    ¹H NMR (400 MHz, CDCl₃) δ 1.35 (s, 12H), 3.18 (s, 3H), 4.36 (s, 2H),    7.41 (d, J=7.6 Hz, 1H), 7.93 (d, J=7.6 Hz, 1H), 8.29 (s, 1H); ¹³C    NMR (125 MHz, CDCl₃) δ 24.8, 29.4, 52.1, 84.0, 121.9, 130.1, 132.3,    137.3, 143.8, 168.5.-   2-Methyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-isoindolin-1-one:    ¹H NMR (400 MHz, CDCl₃) δ 1.35 (s, 12H), 3.19 (s, 3H), 4.35 (s, 2H),    7.81 (d, J=7.6 Hz, 1H), 7.86 (s, 1H), 7.89 (d, J=7.6 Hz, 1H); ¹³C    NMR (125 MHz, CDCl₃) δ 24.9, 29.5, 51.9, 84.2, 122.7, 128.7, 134.3,    135.2, 140.1, 168.6.

(11)N,N-Dimethyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzamideandN,N-dimethyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzamide

-   41% yield [meta/para=13]; white solid; ¹¹3 NMR (130 MHz, CDCl₃) δ    30.6; IR (neat, ν/cm⁻¹) 2978, 1634, 1482, 1356, 1267, 1213, 965,    812, 709, 671; HRMS (ESI⁺) Calcd for C₁₅H₂₂BNNaO₃ ([M+Na]⁺)    298.1585, Found 298.1585.    N,N-Dimethyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzamide:

¹H NMR (500 MHz, CDCl₃) δ 1.34 (s, 12H), 2.96 (s, 3H), 3.10 (s, 3H),7.40 (dd, J=8.0, 8.0 Hz, 1H), 7.49 (ddd, J=8.1, 1.1, 1.1 Hz, 1H),7.82-7.84 (m, 2H); ¹³C NMR (100 MHz, CDCl₃) δ 25.0, 35.4, 39.7, 84.1,127.9, 129.8, 133.2, 135.8, 135.9, 171.8.

-   N,N-Dimethyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzamide:

¹H NMR (400 MHz, CDCl₃) δ 1.35 (s, 12H), 3.19 (s, 3H), 4.35 (s, 2H),7.81 (d, J=7.6 Hz, 1H), 7.86 (s, 1H), 7.89 (d, J=7.6 Hz, 1H); ¹³C NMR(125 MHz, CDCl₃) δ 24.9, 29.5, 51.9, 84.2, 122.7, 128.7, 134.3, 135.2,140.1, 168.6.

N,N-Dimethyl-3,5-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzamide

-   11% yield; white solid; ¹H NMR (400 MHz, CDCl₃) δ 1.33 (s, 24H),    2.95 (s, 3H), 3.09 (s, 3H), 7.93 (d, J=1.3 Hz, 2H), 8.28 (t, J=1.3    Hz, 1H); ¹³C NMR (100 MHz, CDCl₃) δ 25.0, 35.3, 39.8, 84.1, 135.5,    135.9, 142.1, 171.9; ¹¹3 NMR (130 MHz, CDCl₃) δ30.6; IR (neat,    ν/cm⁻¹) 2978, 1636, 1594, 1380, 1330, 1213, 1142, 889, 755, 689;    HRMS (ESI⁺) Calcd for C₂₁H₃₃B₂NNaO₅([M+Na]⁺) 424.2437, Found    424.2455.

(12)1-Piperidinyl(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)methanone

-   50% yield; white solid; ¹H NMR (400 MHz, CDCl₃) δ 1.34 (s, 12H),    1.48-1.51 (m, 2H), 1.63-1.70 (m, 4H), 3.29-3.37 (m, 2H), 3.67-3.73    (m, 2H), 7.38 (dd, J=7.6, 6.7 Hz, 1H), 7.46 (d, J=7.6 Hz, 1H),    7.81-7.82 (m, 2H); ¹³C NMR (100 MHz, CDCl₃) δ 24.7, 25.0, 25.7,    26.6, 43.1, 48.9, 84.1, 127.8, 129.5, 133.1, 135.7, 136.1, 170.4;    ¹¹B NMR (130 MHz, CDCl₃) δ 30.8; IR (neat, ν/cm⁻¹) 2938, 1714, 1626,    1358, 1271, 1143, 1094, 964, 859, 754, 666; HRMS (ESI⁺) Calcd for    C₁₈H₂₆BNNaO₃([M+Na]⁺) 338.1898, Found 338.1897.

1-Piperidinyl(3,5-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2yl)phenyl)methanone:

-   11% yield; white solid; ¹H NMR (400 MHz, CDCl₃) δ 1.37 (s, 24H),    1.49-1.65 (m, 6H), 3.32-3.33 (m, 2H), 3.64-3.70 (m, 2H), 7.89 (s,    2H), 8.27 (s, 1H); ¹³C NMR (100 MHz, CDCl₃) δ 24.7, 25.0, 25.7,    26.6, 43.1, 48.9, 84.1, 135.6, 135.8, 142.1, 170.5; ¹¹B NMR (130    MHz, CDCl₃) δ 30.8; IR (neat, ν/cm⁻¹) 2979, 1624, 1329, 1267, 1142,    966, 889, 755, 716, 666; HRMS (ESI⁺) Calcd for C₂₄H₃₇B₂NNaO₅    ([M+Na]⁺) 464.2750, Found 464.2728.

(13)(2-Bromo-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-4-morpholinylmethanoneand(2-bromo-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-4-morpholinylmethanone

-   88% yield [meta/para=3.2]; pale yellow solid; ¹¹B NMR (130 MHz,    CDCl₃) δ30.8; IR (KBr, ν/cm⁻¹) 2977, 2927, 2857, 1645, 1592, 1434,    1386, 1356, 1280, 1248, 1143, 1114, 1094, 1016, 848, 689; HRMS    (ESI⁺) Calcd for C₁₇H₂₃BBrNNaO₄ ([M+Na]⁺) 418.0801, Found 418.0791.    (2-Bromo-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-4-morpholinylmethanone:    ¹H NMR (500 MHz, CDCl₃) δ 1.30 (s, 12H), 3.10-3.29 (m, 2H),    3.50-3.61 (m, 1H), 3.64-3.80 (m, 4H), 3.80-3.89 (m, 1H), 7.55 (d,    J=8.0 Hz, 1H), 7.62 (dd, J=8.0, 1.8 Hz, 1H), 7.65 (d, J=1.8 Hz, 1H);    ¹³C NMR (125 MHz, CDCl₃) δ 24.9, 41.8, 47.0, 66.5, 66.6, 84.2,    122.4, 132.0, 133.8, 136.4, 138.7, 167.7.-   (2-Bromo-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-4-morpholinylmethanone:    ¹H NMR (500 MHz, CDCl₃) δ 1.28 (s, 12H), 3.10-3.29 (m, 2H),    3.50-3.61 (m, 1H), 3.64-3.80 (m, 4H), 3.80-3.89 (m, 1H), 7.22 (d,    J=7.5 Hz, 1H), 7.74 (d, J=7.5 Hz, 1H), 7.97 (s, 1H); ¹³C NMR (125    MHz, CDCl₃) δ 24.5, 41.8, 47.0, 66.5, 66.6, 84.3, 118.8, 127.0,    133.8, 136.9, 139.8, 167.5.

(14)Azepane-1-yl(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)methanone

-   36% yield; white solid; ¹H NMR (400 MHz, CDCl₃) δ 1.34 (s, 12H),    1.59-1.64 (m, 6H), 1.81-1.85 (m, 2H), 3.36 (t, J=5.4 Hz, 2H), 3.67    (t, J=5.8 Hz, 2H), 7.38 (dd, J=7.9, 7.6 Hz, 1H), 7.46 (d, J=7.9 Hz,    1H), 7.80-7.82 (m, 2H);

¹³C NMR (100 MHz, CDCl₃) δ 25.0, 26.6, 27.4, 28.0, 29.6, 46.3, 49.9,84.1, 127.8, 129.2, 132.8, 135.4, 136.9, 171.7; ¹¹B NMR (130 MHz, CDCl₃)δ 30.6; IR (neat, ν/cm⁻¹) 2977, 2928, 1631, 1409, 1356, 1319, 1216,1099, 859, 708; HRMS (ESI⁺) Calcd for C₁₉H₂₈BNNaO₃ ([M+Na]⁺) 352.2054,Found 352.2049.

Azepane-1-yl(3,5-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)methanone

-   12%; yield; white solid; ¹H NMR (400 MHz, CDCl₃) δ 1.33 (s, 24H),    1.58-1.59 (m, 6H), 1.80-1.86 (m, 2H), 3.36 (t, J=5.4 Hz, 2H), 3.65    (t, J=5.4 Hz, 2H), 7.90 (s, 2H), 8.27 (s, 1H); ¹³C NMR (100 MHz,    CDCl₃) δ 25.0, 26.7, 27.5, 28.1, 29.6, 46.1, 50.0, 84.1, 135.5,    136.3, 141.8, 171.8; ¹¹B NMR (130 MHz, CDCl₃) δ 31.3; IR (neat,    ν/cm⁻¹) 2930, 2927, 1628, 1429, 1389, 1270, 1142, 889, 754, 689;    HRMS (ESI⁺) Calcd for C₂₅H₃₉B₂NNaO₅ ([M+Na]⁺) 478.2907, Found    478.2926.

(15)N,N-Dihexyl-2-(trifluoromethyl)-5-(4,4,6-trimethyl-1,3,2-dioxaborolan-2-yl)benzamideandN,N-dihexyl-2-(trifluoromethyl)-4-(4,4,6-trimethyl-1,3,2-dioxaborolan-2-yl)benzamide

-   62% yield [meta/para=5.3]; colorless oil; ¹¹B NMR (130 MHz, CDCl₃) δ    26.2; IR (neat, ν/cm⁻¹) 2931, 1644, 1502, 1408, 1306, 1170, 1039,    844, 767, 687; HRMS (ESI⁺) Calcd for C₂₆H₄₁BF₃NNaO₃([M+Na]⁺)    506.3024, Found 506.3013.-   N,N-Dihexyl-2-(trifluoromethyl)-5-(4,4,6-trimethyl-1,3,2-dioxaborolan-2-yl)benzamide:    ¹H NMR (500 MHz, CDCl₃) δ 0.81 (t, J=7.2 Hz, 3H), 0.89-0.92 (m, 3H),    1.08-1.09 (m, 4H), 1.17-1.21 (m, 2H), 1.33-1.47 (m, 18H), 1.61-1.64    (m, 2H), 1.86-1.91 (m, 1H), 2.95-3.00 (m, 2H), 3.12-3.19 (m, 1H),    3.77-3.84 (m, 1H), 4.13-4.37 (m, 1H), 7.60 (d, J=7.6 Hz, 1H), 7.75    (s, 1H), 7.87 (d, J=7.6 Hz, 1H); ¹³C NMR (100 MHz, CDCl₃) δ 14.0,    14.1, 22.5, 22.7, 23.1, 26.2, 26.4, 26.9, 28.0, 28.2, 31.2, 31.4,    31.7, 44.4, 46.0, 48.7, 65.4, 71.6, 124.0 (q, J=274 Hz), 125.2 (q,    J=3.6 Hz), 126.4, 127.6 (q, J=32.3 Hz), 132.9, 133.9, 169.2; ¹⁹F NMR    (368 MHz, CDCl₃) δ −61.9.    N,N-Dihexyl-2-(trifluoromethyl)-4-(4,4,6-trimethyl-1,3,2-dioxaborolan-2-yl)benzamide:    ¹H NMR (500 M Hz, CDCl₃) δ 0.81 (t, J=7.2 Hz, 3H), 0.89-0.92 (m,    3H), 1.08-1.09 (m, 4H), 1.17-1.21 (m, 2H), 1.33-1.47 (m, 18H),    1.61-1.64 (m, 2H), 1.86-1.91 (m, 1H), 2.95-3.00 (m, 2H), 3.12-3.19    (m, 1H), 3.77-3.84 (m, 1H), 4.13-4.37 (m, 1H), 7.26 (d, J=6.7 Hz,    1H), 7.96 (d, J=6.7 Hz, 1H), 8.08 (s, 1H); ¹³C NMR (100 MHz, CDCl₃)    δ 14.0, 14.1, 22.4, 22.7, 23.1, 26.2, 26.4, 26.9, 28.0, 28.2, 31.2,    31.3, 31.7, 44.4, 46.0, 48.7, 65.4, 71.6, 124.3 (q, J=296 Hz),    125.7, 127.6 (q, J=32.3 Hz), 131.8 (q, J=4.8 Hz), 134.6, 169.2; ¹⁹F    NMR (368 MHz, CDCl₃) 6 -61.5.

(16)3-Fluoro-N,N-dihexyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzamideand3-fluoro-N,N-dihexyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzamide

-   99% yield [meta/para=7.7]; colorless oil; ¹¹H NMR (130 MHz, CDCl₃) δ    30.0; IR (neat, ν/cm⁻¹) 2929, 1633, 1368, 1143, 1099, 968, 923, 854,    756, 676; HRMS (ESI⁺) Calcd for C₂₅H₄₁FNNaO₃ ([M+Na]⁺) 456.3056,    Found 456.3035.    3-Fluoro-N,N-dihexyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzamide:    ¹H NMR (400 MHz, CDCl₃) δ 0.82 (t, J=6.7 Hz, 3H), 0.89-0.91 (m, 3H),    1.12-1.17 (m, 4H), 1.21-1.49 (m, 22H), 1.61-1.62 (m, 2H), 3.14 (t,    J=7.2 Hz, 2H), 3.44 (t, J=7.2 Hz, 2H), 7.13 (d, J=8.8 Hz, 1H), 7.48    (d, J=8.8 Hz, 1H), 7.55 (s, 1H); ¹³C NMR (100 MHz, CDCl₃) δ 14.0,    14.1, 22.5, 22.7, 24.9, 26.2, 26.8, 27.5, 28.7, 31.3, 31.7, 45.0,    49.1, 84.3, 116.5 (d, J=22.6 Hz), 121.6 (d, J=19.7 Hz), 128.2 (d,    J=2.8 Hz), 138.9 (d, J=6.6 Hz), 162.2 (d, J=248 Hz), 170.1;

¹⁹F NMR (368 MHz, CDCl₃) δ −115.3 (s, 1F).3-Fluoro-N,N-dihexyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzamide:¹H NMR (400 MHz, CDCl₃) δ 0.82 (t, J=6.7 Hz, 3H), 0.89-0.91 (m, 3H),1.12-1.18 (m, 4H), 1.21-1.49 (m, 22H), 1.61-1.62 (m, 2H), 3.14 (t, J=7.2Hz, 2H), 3.44 (t, J=7.2 Hz, 2H), 7.01 (d, J=9.0 Hz, 1H), 7.11 (d, J=9.0Hz, 1H), 7.73-7.77 (m, 1H); ¹³C NMR (100 MHz, CDCl₃) δ 14.0, 14.1, 22.5,22.7, 24.9, 26.2, 26.8, 27.5, 28.7, 31.3, 31.7, 44.8, 49.0, 84.2, 113.6(d, J=26.3 Hz), 132.0 (br), 137.1 (d, J=8.4 Hz), 142.4 (d, J=7.5 Hz),165.4 (d, J=253 Hz), 169.9; ¹⁹F NMR (368 MHz, CDCl₃) δ −103.7 (s, 1F).

(17)3-Bromo-N,N-dihexyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzamide

-   86% yield; pale yellow oil; ¹H NMR (400 MHz, CDCl₃) δ 0.83 (t, J=7.2    Hz, 3H), 0.89-0.91 (m, 3H), 1.12-1.17 (m, 4H), 1.21-1.33 (m, 20H),    1.49-1.63 (m, 4H), 3.13 (t, J=7.6 Hz, 2H), 3.43 (t, J=7.6 Hz, 2H),    7.56 (s, 1H), 7.69 (s, 1H), 7.93 (s, 1H); ¹³C NMR (100 MHz, CDCl₃)    δ14.0, 14.1, 22.5, 22.7, 24.9, 26.2, 26.8, 27.5, 28.7, 31.3, 31.7,    45.0, 49.1, 84.4, 122.4, 131.0, 132.1, 138.0, 138.8, 169.9; ¹¹B NMR    (130 MHz, CDCl₃) δ 30.7; IR (neat, ν/cm⁻¹) 2929, 2857, 1635, 1435,    1348, 1143, 965, 964, 885, 704; HRMS (ESI⁺) Calcd for C₂₅H₄₁BBrNNaO₃    ([M+Na]⁺) 516.2255, Found 516.2255.

(18)N,N-Dihexyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-[1,1′-biphenyl]-3-carboxamide

-   81% yield; pale yellow oil; ¹H NMR (400 MHz, CDCl₃) δ 0.79 (t, J=7.2    Hz, 3H), 0.90-0.92 (m, 3H), 1.11-1.19 (m, 6H), 1.23-1.35 (m, 18H),    1.51-1.53 (m, 2H), 1.63-1.66 (m, 2H), 3.20 (t, J=7.6 Hz, 2H), 3.48    (t, J=8.1 Hz, 2H), 7.34 (t, J=7.4 Hz, 1H), 7.43 (dd, J=8.1, 7.4 Hz,    2H), 7.62 (d, J=8.1 Hz, 2H), 7.66 (s, 1H), 7.76 (s, 1H), 8.05 (s,    1H); ¹³C NMR (100 MHz, CDCl₃) δ 14.1, 14.2, 22.5, 22.8, 25.0, 26.3,    27.0, 27.7, 28.9, 31.4, 31.8, 45.0, 49.3, 84.2, 127.3, 127.6, 128.0,    128.8, 131.6, 134.1, 137.5, 140.6, 140.8, 171.6; ¹¹B NMR (130 MHz,    CDCl₃) δ 32.5; IR (neat, ν/cm⁻¹) 2929, 2857, 1634, 1411, 1321, 1144,    966, 894, 756, 698; HRMS (ESI⁺) Calcd for C₃₁H₄₆BNNaO₃ ([M+Na]⁺)    514.3463, Found 514.3456.

(19)3-Cyano-N,N-dihexyl-5-(4,4,5,5-tetramethyl⁻1,3,2⁻dioxaborolan-2-yl)benzamide

-   87% yield; pale yellow oil; ¹H NMR (400 MHz, CDCl₃) δ 0.82 (t, J=7.2    Hz, 3H), 0.88-0.90 (m, 3H), 1.11-1.42 (m, 24H), 1.48-1.52 (m, 2H),    1.65-1.69 (m, 2H), 3.11 (t, J=7.6 Hz, 2H), 3.43 (t, J=7.6 Hz, 2H),    7.69 (dd, J=1.6, 1.6 Hz, 1H), 7.97 (dd, J=1.6, 1.4 Hz, 1H), 8.08    (dd, J=1.6, 1.4 Hz, 1H); ¹³C NMR (100 MHz, CDCl₃) δ 14.0, 14.1,    22.4, 22.6, 24.9, 26.2, 26.8, 27.5, 28.7, 31.2, 31.6, 45.1, 49.2,    84.8, 112.4, 118.2, 132.3, 136.6, 137.9, 138.7, 169.2; ¹¹B NMR (130    MHz, CDCl₃) δ 30.3; IR (neat, ν/cm⁻¹) 2930, 2857, 2231, 1637, 1371,    1265, 1143, 966, 850, 704; HRMS (ESI⁺) Calcd for C₂₆H₄₁BN₂NaO₃    ([M+Na]⁺) 463.3102, Found 463.3124.

(20)2,3-Dichloro-N,N-dihexyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzamide

-   94% yield; pale yellow oil; ¹H NMR (500 MHz, CDCl₃) δ 0.81 (t, J=7.5    Hz, 3H), 0.91 (t, J=6.7 Hz, 3H), 1.08-1.11 (m, 4H), 1.18-1.21 (m,    2H), 1.32-1.50 (m, 20H), 1.65-1.70 (m, 2H), 2.98-3.02 (m, 1H),    3.05-3.09 (m, 1H), 3.26-3.31 (m, 1H), 3.64-3.70 (m, 1H), 7.56 (d,    J=1.2 Hz, 1H), 7.85 (d, J=1.2 Hz, 1H); ¹³C NMR (100 MHz, CDCl₃) δ    14.0, 14.1, 22.4, 22.7, 24.9 (br), 26.2, 26.8, 27.3, 28.3, 31.2,    31.7, 44.7, 48.5, 84.6, 131.6, 131.9, 133.1, 136.3, 138.4, 167.3;    ¹¹B NMR (130 MHz, CDCl₃) 830.4; IR (neat, ν/cm⁻¹) 2930, 2858, 1644,    1467, 1350, 1268, 1142, 965, 894, 755; HRMS (ESI⁺) Calcd for    C₂₅H₄₀BCl₂NNaO₃ ([M+Na]⁺) 506.2371, Found 506.2394.

(21)2-Fluoro-N,N-dihexyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-3-(trifluoromethyl)benzamide

-   89% yield; pale yellow oil; ¹H NMR (400 MHz, CDCl₃) δ 0.80 (t, J=7.2    Hz, 3H), 0.90 (t, J=6.7 Hz, 3H), 1.08-1.11 (m, 4H), 1.17-1.22 (m,    2H), 1.33-1.49 (m, 20H), 1.65-1.67 (m, 2H), 3.14 (t, J=7.6 Hz, 2H),    3.40-3.64 (m, 2H), 7.94 (d, J=6.3 Hz, 1H), 8.05 (d, J=7.2 Hz, 1H);

¹³C NMR (100 MHz, CDCl₃) δ 13.9, 14.1, 22.4, 22.6, 24.9, 26.1, 26.7,27.4, 28.4, 31.2, 31.7, 44.9, 48.8, 84.7, 118.4 (qd, J=33.6, 12.0 Hz),122.5 (q, J=272 Hz), 126.6 (d, J=18.0 Hz), 134.1 (d, J=3.6 Hz), 139.2(d, J=4.8 Hz), 157.3 (d, J=260 Hz), 165.0; ¹⁹F NMR (368 MHz, CDCl₃) δ−115.4 (s, 1F), −63.1 (s, 3F); ¹¹B NMR (130 MHz, CDCl₃) δ 30.1; IR(neat, ν/cm⁻¹) 2931, 1644, 1468, 1385, 1302, 1239, 1197, 914, 756, 672;HRMS (ESI⁺) Calcd for C₂₆H₄₀BF₄NNaO₃ ([M+Na]⁺) 524.2930, Found 524.2939.

(22)N,N-Dihexyl-2-(5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)thiophene)carboxamide

-   51% yield; pale yellow oil; ¹H NMR (500 MHz, CDCl₃) δ 0.80-0.92 (m,    6H), 1.16-1.38 (m, 12H), 1.33 (s, 12H), 1.53-1.70 (m, 4H), 3.38-3.44    (m, 4H), 7.30 (d, J=3.6 Hz, 1H), 7.50 (d, J=3.6 Hz, 1H); ¹³C NMR    (125 MHz, CDCl₃) δ 13.9 (2C), 22.5, 24.7 (2C), 26.4 (br, 2C), 27.5    (br), 28.8 (br), 31.4 (2C), 46.1 (br), 49.3 (br), 84.3, 129.1,    136.3, 144.2, 164.3; ¹¹B NMR (130 MHz, CDCl₃) δ 29.0; IR (neat,    ν/cm⁻¹) 2956, 2929, 2862, 1625, 1525, 1463, 1419, 1372, 1350, 1287,    1270, 1210, 1143, 1063, 1021, 997, 857, 853, 820, 739, 687, 667;    HRMS (ESI⁺) Calcd for C₂₃H₄₀BNNaO₃S ([M+Na]⁺) 444.2720, Found    444.2731.

N,N-Dihexyl-2-(3,5-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)thiophene)carboxamide

-   14% yield; pale brown oil; ¹H NMR (500 MHz, CDCl₃) δ 0.75-0.96 (m,    6H), 1.03-1.53 (m, 40H), 3.05-3.22 (m, 2H), 3.35-3.55 (m, 2H), 7.83    (s, 1H); ¹³C NMR (125 MHz, CDCl₃) δ 13.97, 14.03, 22.4, 22.6, 24.7,    24.8, 26.2, 26.9, 27.0, 28.3, 31.3, 31.7, 45.2, 49.0, 83.6, 84.2,    143.1, 153.2, 165.5; ¹¹B NMR (130 MHz, CDCl₃) δ 28.6; IR (neat,    ν/cm⁻¹) 3424, 2929, 2859, 1633, 1536, 1455, 1371, 1321, 1268, 1213,    1139, 1111, 1028, 1002, 967, 911, 882, 851, 829, 727, 688, 666; HRMS    (ESI⁺) Calcd for C₂₉H₅₁B₂NNaO₅S ([M+Na]⁺) 570.3572, Found 570.3551.

(23)N,N-Dihexyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrrole-2-carboxamide

-   79% yield; colorless oil; ¹H NMR (400 MHz, CDCl₃) δ 0.81-0.93 (m,    6H), 1.23-1.36 (m, 24H), 1.53-1.78 (m, 4H), 3.25-3.70 (m, 4H),    6.43-6.70 (m, 1H), 6.74-6.78 (m, 1H), 9.85 (brs, 1H); ¹³C NMR (125    MHz, CDCl₃) δ 14.0 (2C), 22.5, 24.7 (2C), 26.6 (2C), 27.6 (br), 28.8    (br), 31.5 (2C), 47.2 (br), 48.5 (br), 83.8, 111.6, 120.2, 129.2,    161.5;

¹¹B NMR (130 MHz, CDCl₃) δ 28.3; IR (neat, ν/cm⁻¹) 3441, 3256, 2929,2858, 1610, 1553, 1467, 1424, 1345, 1300, 1265, 1219, 1144, 973, 855,790, 759, 704; HRMS (BSI⁺) Calcd for C₂₃H₄₁BN₂NaO₃ ([M+Na]⁺) 427.3108,Found 427.3114.

(24)N,N-Dihexyl-(1-methyl-5-(4,4,5,5-tetramethyl⁻1,3,2-dioxaborolan-2-yl)-1H-pyrrole)-2-carboxamideandN,N-dihexyl-(1-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrrole)-2⁻carboxamide

-   74% yield [5−/4−=6.7]; pale yellow oil; ¹¹B NMR (130 MHz, CDCl₃) δ    28.3; IR (neat, ν/cm⁻¹) 2929, 2858, 1628, 1531, 1467, 1416, 1373,    1302, 1265, 1145, 1108, 1091, 965, 858, 754, 692; HRMS (ESI⁺) Calcd    for C₂₄H₄₃BN₂NaO₃ ([M+Na]⁺) 441.3264, Found 441.3255.    N,N-Dihexyl-(1-methyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrrole)-2-carboxamide:    ¹H NMR (500 MHz, CDCl₃) δ 0.78-0.94 (m, 6H), 1.10-1.40 (m, 24H),    1.42-1.75 (m, 4H), 3.26-3.54 (m, 4H), 3.82 (s, 3H), 6.20 (d, J=4.0    Hz, 1H), 6.70 (d, J=4.0 Hz, 1H); ¹³C NMR (125 MHz, CDCl₃) δ 13.9    (2C), 22.5 (2C), 24.7, 26.4 (br, 2C), 27.5 (br), 28.6 (br), 31.4    (2C), 34.6, 44.6 (br), 48.9 (br), 83.2, 109.7, 120.2, 132.5, 164.5.    N,N-Dihexyl-(1-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrrole)-2-carboxamide:    ¹H NMR (500 MHz, CDCl₃) δ 0.78-0.94 (m, 6H), 1.10-1.40 (m, 24H),    1.42-1.75 (m, 4H), 3.26-3.54 (m, 4H), 3.71 (s, 3H), 6.56-6.60 (m,    1H), 7.04-7.11 (m, 1H); ¹³C NMR (125 MHz, CDCl₃) δ 13.9 (2C), 22.5    (2C), 24.7, 26.4 (2C), 27.5 (br), 28.6 (br), 31.4 (2C), 35.6, 44.6    (br), 48.9 (br), 82.9, 117.0, 127.6, 134.0, 164.0.

(25)N,N-Dihexyl-(7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole)-2-carboxamide

-   71% yield; pale yellow oil; ¹H NMR (500 MHz, CDCl₃) δ 0.87-0.96 (m,    6H), 1.30-1.41 (m, 12H), 1.39 (s, 12H), 1.60-1.85 (m, 4H), 3.30-3.90    (m, 4H), 6.75 (d, J=2.3 Hz, 1H), 7.15 (t, J=8.0 Hz, 1H), 7.75 (d,    J=8.0 Hz, 1H), 7.78 (d, J=8.0 Hz, 1H), 9.94 (brs, 1H); ¹³C NMR (125    MHz, CDCl₃) δ 14.0 (2C), 22.5 (2C), 24.9, 26.6 (br, 2C), 27.6 (br),    28.8 (br), 31.5 (2C), 47.4 (br), 49.0 (br), 83.9, 103.9, 119.9,    125.3, 126.9, 129.9, 131.7, 140.0, 162.5; ¹¹B NMR (130 MHz, CDCl₃) δ    31.2; IR (neat, ν/cm⁻¹) 3438, 3056, 2927, 2857, 1615, 1595, 1529,    1463, 1443, 1369, 1288, 1200, 1146, 1130, 1110, 1045, 979, 849, 813,    748, 734, 678; HRMS (ESI⁺) Calcd for C₂₇H₄₃BN₂NaO₃ ([M+Na]⁺)    477.3264 Found 477.3264.

(26)N,N-Dimethyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)picolinamideandN,N-dimethyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)picolinamide

-   43% yield [4−/5−=3.6]; white solid; ¹³C NMR (100 MHz, CDCl₃) 8 (4-    and 5-position isomers) 25.0 (4- and 5-position isomers), 35.71,    35.76, 39.0, 39.1, 84.6, 84.8, 122.7, 128.5, 129.3, 143.4, 147.9,    154.07, 154.13, 156.5, 169.4 (4- and 5-position isomers); ¹¹B NMR    (130 MHz, CDCl₃) δ 30.6; IR (neat, ν/cm⁻¹) 2979, 1640, 1473, 1358,    1263, 1105, 965, 857, 752, 672; HRMS (ESI⁺) Calcd for    C₁₄H₂₁BN₂N₂NaO₃ ([M+Na]⁺) 299.1537, Found 299.1534.    N,N-Dimethyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)picolinamide:    ¹H NMR (500 MHz, CDCl₃) δ 1.34 (s, 12H), 3.04 (s, 3H), 3.13 (s, 3H),    7.65 (d, J=5.8 Hz, 1H), 7.96 (s, 1H), 8.60 (d, J=5.8 Hz, 1H).    N,N-Dimethyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)picolinamide:    ¹H NMR (500 MHz, CDCl₃) δ 1.36 (s, 12H), 3.04 (s, 3H), 3.13 (s, 3H),    7.58 (d, J=7.8 Hz, 1H), 8.15 (d, J=7.8 Hz, 1H), 8.91 (s, 1H).

As can be seen from the above-described results, the borylation ofaromatic compounds by the catalyst of the present invention results inthe meta-selective borylation. [0182]

-   (27) Table 1 shows the meta-para selectivity (m/p) in the case where    the borylation reaction was performed in the same manner as Example    9(1) by using the ligands described in Examples 2 to 6.

TABLE 1 R² X m/p n-Hex O m/p = 7.4

O m/p = 14

O m/p = 7.2

O m/p = 3.9

O m/p = 3.6

Example 10

-   l (1) The borylation reaction was performed by using    alkoxycarbonyl-substituted pyridines and    alkoxycarbonylmethyl-substituted pyridines as the substituted    aromatic compounds, the substrates of the borylation reaction, in    the same manner as Example 9(1).

In a dried test tube, to a p-xylene (1.5 mL) solution of analkoxycarbonyl-substituted pyridine (1.00 equiv), [Ir(OMe)(cod)]₂ (1.5mol %),1-(2-([2,2′-bipyridin]-5-yl)phenyl)-3-(4-trifluoromethylphenyl)urea (3.0mol %) and bis(pinacolato)diboron (1.5 equiv) were added and stirred at25° C. for 18 hours. The solvent was removed under reduced pressure, andthen the products were isolated and prepared by recycling preparativeHPLC.

The obtained compounds were as follows.

-   Ethyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine-2-carboxylate    and    ethyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine-2-carboxylate

70% yield [5−/4−=5.0]; white solid; ¹³C NMR (100 MHz, CDCl₃) δ (4- and5-position isomers) 25.0 (4- and 5-position isomers), 35.71, 35.76,39.0, 39.1, 84.6, 84.8, 122.7, 128.5, 129.3, 143.4, 147.9, 154.07,154.13, 156.5, 169.4 (4- and 5-position isomers); ¹¹B NMR (130 MHz,CDCl3) δ 30.6; IR (neat, ν/cm⁻¹) 2979, 1640, 1473, 1358, 1263, 1105,965, 857, 752, 672; HRMS (ESI⁺) Calcd for C₁₄H₂₁BN₂NaO₃ ([M+Na]⁺)299.1537, Found 299.1534.Ethyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan⁻2⁻yl)pyridine-2-carboxylate: ¹H NMR (500 MHz, CDCl₃) δ 1.36 (s, 12H), 3.04 (s, 3H),3.13 (s, 3H), 7.58 (d, J=7.8 Hz, 1H), 8.15 (d, J=7.8 Hz, 1H), 8.91 (s,1H). Ethyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan⁻2⁻yl)pyridine-2-carboxylate: ¹H NMR (500 MHz, CDCl₃) δ 1.34 (s, 12H), 3.04 (s, 3H),3.13 (s, 3H), 7.65 (d, J=5.8 Hz, 1H), 7.96 (s, 1H), 8.60 (d, J=5.8 Hz,1H). By using the ligand used in (1), the following compounds wereobtained in the same manner as the method of (1).

-   (2)    2-Ethoxycarbonylmethyl-5-(4,4,5,5-tetramethyl⁻1,3,2⁻dioxaborolan-2-yl)pyridine    and    2-ethoxycarbonylmethyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine

-   64% yield [5−/−4−=1.7]; pale brown oil; ¹¹B NMR (130 MHz, CDCl₃) δ    30.9; IR (neat, ν/cm⁻¹) 2980, 2934, 1739, 1600, 1557, 1480, 1403,    1371, 1258, 1166, 1145, 1099, 1028, 964, 856, 668; HRMS (ESI⁺) Calcd    for C₁₅H₂₂BNNaO₄ ([M+Na]⁺) 314.1540, Found 314.1539.-   2-Ethoxycarbonylmethyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine:    ¹H NMR (500 MHz, CDCl₃) δ 1.18-1.25 (m, 3H), 1.32 (s, 12 H), 3.83    (s, 2H), 4.10-4.20 (m, 2H), 7.26 (d, J=8.0 Hz, 1H), 8.00 (d, J=8.0    Hz, 1H), 8.86 (s, 1H); ¹³C NMR (100 MHz, CDCl₃) δ 14.1, 24.7, 44.1,    61.0, 84.1, 123.1, 142.9, 155.2, 156.8, 170.4.-   2-Ethoxycarbonylmethyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine:    ¹H NMR (500 MHz, CDCl₃) δ 1.18-1.25 (m, 3H), 1.32 (s, 12 H), 3.82    (s, 2H), 4.10-4.20 (m, 2H), 7.50 (d, J=4.6 Hz, 1H), 7.60 (s, 1H),    8.56 (d, J=4.6 Hz, 1H); ¹³C NMR (100 MHz, CDCl₃) 6 14.1, 24.8, 43.8,    60.9, 84.4, 127.0, 128.9, 148.9, 153.8, 170.7.

Example 11

-   (1) The borylation reaction was performed by using a phosphate-,    phosphinediamide- or phosphine oxide-substituted benzene as the    substituted aromatic compound, the substrate of the borylation    reaction, in the same manner as Example 9.

In a dried test tube, to a p-xylene (1.5 mL) solution of a phosphate-,phosphinediamide- or phosphine oxide-substituted benzene (1.00 equiv),[Ir(OMe)(cod)]₂ (1.5 mol %),1-(2-([2,2′-bipyridin]-5-yl)phenyl)-3-cyclohexylurea (3.0 mol %) andbis(pinacolato)diboron (1.5 equiv) were added and stirred at 25° C. or40° C. for 16 hours. The solvent was removed under reduced pressure, andthen the products were isolated and prepared by recycling preparativeHPLC.

(wherein R represents an ethoxy group, a diethylamino group or acyclohexyl group(abbreviated as Cy), and Y represents H, Br, Cl, CF₃,OMe or Me).

The obtained compounds were as follows.

-   3-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)phenyldiethylphosphonate    and    4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyldiethylphosphonate

-   41% yield [meta/para=17]; colorless solid; ¹¹B NMR (130 MHz, CDCl3)    δ 30.7; ³¹P NMR (158 MHz, CDCl₃) δ 28.5, 28.1; IR (KBr, ν/cm⁻¹)    2980, 1599, 1481, 1408, 1390, 1358, 1324, 1243, 1211, 1133,    1136,1097, 1055, 1027, 965, 869, 843, 795, 767, 704, 669; HRMS    (ESI⁺) Calcd for C₁₆H₂₆BO₅P ([M+Na]⁺) 363.1509, Found 363.1498.

3-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)phenyldiethylphosphonate:

¹H NMR (400 MHz, CDCl₃) δ 1.30 (t, J=7.2 Hz, 6H), 1.32 (s, 12H),3.98-4.18 (m, 4H), 7.44 (ddd, J=7.6, 7.6, 4.0 Hz, 1H), 7.88 (ddd,J=13.0, 7.6, 1.3 Hz, 1H), 7.95 (dd, J=7.6, 1.3 Hz, 1H),8.24 (d, J=13.0Hz, 1H), ¹³C NMR (100 MHz, CDCl₃) δ 16.3 (d, J_(C-P)=6.6 Hz), 24.8, 62.0(d, J_(C-P)=5.8 Hz), 84.0, 127.6 (d, J_(C-P)=187 Hz), 127.7 (d,J_(C-P)=15.0 Hz), 134.3 (d, J_(C-P)=10.3 Hz), 138.0 (d, J_(C-P)=9.4Hz),138.6 (d, J_(C-P)2.8 Hz).

-   4-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)phenyldiethylphosphonate:

¹H NMR (400 MHz, CDCl₃) δ 1.30 (t, J=7.2 Hz, 6H),1.32 (s, 12H),3.98-4.18 (m, 4H), 7.78 (dd, J=13.0, 8.0 Hz, 2H),7.88 (dd, J=8.0, 4.0Hz, 2H); ¹³C NMR (100 MHz, CDCl₃) δ 16.3 (d, J_(C-P)=6.6 Hz), 24.8, 62.0(d, J_(C-P)=5.8 Hz), 84.0, 130.9 (d, J_(C-P)=185 Hz), 130.8 (d,J_(C-P)=9.4 Hz), 134.5 (d, J_(C-P)=15.0 Hz).

-   3,5-Bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyldiethylphosphonate

-   16% yield; colorless solid; ¹H NMR (400 MHz, CDCl₃) δ 1.31 (t, J=7.2    Hz, 6H), 1.33 (s, 24H), 3.99-4.20 (m, 4H), 8.32 (dd, J=13.0, 1.4 Hz,    1H), 8.40 (d, J=1.4 Hz, 1H); ¹³C NMR (100 MHz, CDCl₃) δ 16.3 (d,    J_(C-P)=6.6 Hz), 24.8, 62.0 (d, J_(C-P)=5.6 Hz), 84.0, 127.0 (d,    J_(C-P)=187 Hz), 140.7 (d, J_(C-P)=10.3 Hz), 144.9 (d, J_(C-P)=1.9    Hz); ¹¹B NMR (130 MHz, CDCl3) δ 31.0; ³¹P NMR (158 MHz, CDCl₃) δ    30.4; IR (KBr, ν/cm⁻¹) 2977, 1597, 1389, 1331, 1318, 1272, 1248,    1214, 1168, 1141, 1048, 1019, 964, 952, 886, 848, 790, 718, 691,662;    HRMS (ESI⁺) Calcd for C₂₂H₃₇B₂NaO₇P ([M+Na]⁺) 489.2361, Found    489.2364.-   By using the ligand used in (1), the following compounds ((2) to    (9)) were obtained in the same manner as the method of (1).-   (2)    (2-Methoxy-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyldiethylphosphonate    and    (2-methoxy-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyldiethylphosphonate

-   59% yield [meta/para=0.54]; pale brown oil; ¹¹B NMR (130 MHz, CDCl₃)    δ 30.7; ³¹P NMR (158 MHz, CDCl₃) δ 28.1, 28.5; IR (neat, ν/cm ¹)    2979, 2935, 2909, 1597, 1550, 1492, 1462, 1393, 1357,1325, 1244,    1164, 1146, 1108, 1078, 1055, 1029, 965, 903, 851, 777, 760, 692,    675; HRMS (ESI⁺) Calcd for C₁₇H₂₈BNaO₆P ([M+Na]⁺) 393.1614, Found    393.1599.-   (2-Methoxy-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyldiethylphosphonate:

¹H NMR (500 MHz, CDCl₃) δ 1.15-1.45 (m, 18H), 3.88 (s, 3H), 4.00-4.25(m, 4H), 6.85-6.92 (m, 1H), 7.91 (d, J=8.6 Hz, 1H),8.24 (d, J=14.9 Hz,1H), ¹³C NMR (125 MHz, CDCl₃) δ 16.3, 24.8, 55.6, 62.0 (d, J_(C-P)=4.8Hz), 83.7, 110.3 (d, J_(C-P)=8.4 Hz), 115.8 (d, J_(C-P)=186 Hz), 141.1,142.0 (d, J_(C-P)=7.2 Hz), 163.5 (d, J_(C-P)=2.4 Hz).(2-Methoxy-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyldiethylphosphonate:

¹H NMR (500 MHz, CDCl₃) δ 1.15-1.45 (m, 18H), 3.91 (s, 3H), 4.00-4.25(m, 4H), 7.31 (d, J=6.3 Hz, 1H), 7.41 (dd, J=7.5, 3.4 Hz, 1H), 7.78 (dd,J=14.3, 7.5 Hz, 1H); ¹³C NMR (125 MHz, CDCl₃) δ 16.2, 24.8, 55.8, 62.1(d, J_(C-P)=6.0 Hz), 84.1, 116.5 (d, J_(C-P)=8.4 Hz), 119.0 (d,J_(C-P)=185 HZ), 126.5 (d, J_(C-P)=14.4 Hz), 134.2 (d, J_(C-P)=7.2 Hz),160.5(d, J_(C-P)=2.4 Hz).

(3)(2-Methyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyldiethylphosphonateand(2-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyldiethylphosphonate

-   66% yield [meta/para=9.0]; pale yellow oil; ¹¹B NMR (130 MHz, CDCl₃)    δ 30.9; ³¹P NMR (158 MHz, CDCl₃) δ 30.7, 30.2; IR (neat, ν/cm⁻¹)    2979, 2931, 2906, 1603, 1480, 1445, 1386, 1360, 1317,1248, 1165,    1147, 1109, 1049, 1023, 963, 851, 795, 728, 674; HRMS (ESI⁺) Calcd    for C₁₇H₂₈BNaO₅P ([M+Na]⁺) 377.1665, Found 337.1666.-   (2-Methyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyldiethylphosphonate:

¹H NMR (500 MHz, CDCl₃) δ 1.23-1.38 (m, 18H), 2.56 (s, 3H),4.01-4.18 (m,4H), 7.24 (dd, J=7.5, 5.2 Hz, 1H), 7.81 (d, J=7.5 Hz, 1H), 8.33 (d,J=14.4 Hz, 1H); ¹³C NMR (100 MHz, CDCl₃) δ 16.2 (d, J_(C-P)=6.1 Hz),21.4 (d, J_(C-P)=3.3 Hz), 24.8, 61.7 (d, p=5.6 Hz), 83.8, 126.2 (d,J_(C-P)=183 Hz), 130.5 (d, J_(C-P)=14.1 Hz), 138.6 (d, J_(C-P)=2.8 Hz),140.4 (d, J_(C-P)=10.3 Hz), 144.8 (d, J_(C-P)=10.3 Hz).

-   (2-Methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyldiethylphosphonate:

¹H NMR (500 MHz, CDCl₃) δ 1.23-1.38 (m, 18H), 2.56 (s, 3H), 4.00-4.17(m, 4H), 7.65-7.70 (m, 2H), 7.88 (dd, J=14.3, 8.0 Hz, 1H); ¹³C NMR (100MHz, CDCl₃) δ 16.2 (d, J_(C-P)=6.6 Hz), 20.9 (d, J_(C-P)=2.8 Hz), 24.8,61.7 (d, J_(C-P)=5.6 Hz), 84.0, 129.4 (d, J_(C-P)=181 Hz), 131.5 (d,J_(C-P)=14.4 Hz), 133.0 (d, J_(C-P)=10.8 Hz), 137.2 (d, J_(C-P)=14.4Hz), 140.7 (d, J_(C-P)=10.8 Hz).

(4)(2-Bromo-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)diethylphosphonate

-   65% yield; pale yellow oil; ¹H NMR (400 MHz, CDCl₃) δ 1.29 (s, 12H),    1.32 (t, J=7.2 Hz, 6H), 4.02-4.22 (m, 4H), 7.63 (dd, J=8.1, 4.9 Hz,    1H), 7.73 (dd, J=8.1, 1.3 Hz, 1H), 8.41 (d, J=13.9, 1.3 Hz, 1H); ¹³C    NMR (125 MHz, CDCl₃) δ 16.2 (d, J_(C-P)=7.2 Hz), 24.8, 62.4 (d,    J_(C-P-p)=4.8 Hz), 84.2, 128.6 (d, J_(C-P)=4.8 Hz), 128.7 (d,    J_(C-P)=191 Hz), 133.6 (d, J_(C-P)=9.6 Hz),139.5 (d, J_(C-P)=2.4    Hz), 142.6 (d, J_(C-P)=8.4 Hz); ¹¹B NMR (130 MHz, CDCl₃) δ 30.9;

³¹P NMR (158 MHz, CDCl₃) δ 26.1; IR (neat, ν/cm⁻¹) 2979, 2932, 2906,1585, 1552,1476, 1444, 1373, 1356, 1319, 1262, 1251, 1214, 1166, 1145,1098, 1054, 1024, 964,845, 796, 766, 726, 671; HRMS (ESI⁺) Calcd forC₁₆H₂₅BBrNaO₅P ([M+Na]⁺) 441.0614, Found 441.0602.

(5)(5-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)-2-trifluoromethylphenyl)diethylphosphonate

-   30% yield; pale yellow solid; ¹H NMR (500 MHz, CDCl₃) δ 1.28-1.40    (m, 18H), 4.07-4.26 (m, 4H), 7.78 (dd, J=8.0, 5.7 Hz, 1H), 8.05 (d,    J=8.0 Hz, 1H), 8.64 (d, J=14.9 Hz, 1H); ¹³C NMR (100 MHz, CDCl₃) δ    16.1 (d, J_(C-P)=6.6 Hz), 24.8, 62.6 (d, J_(C-P)=6.1 Hz), 84.5,    121.9 (qd, J_(C-P), C-P=273, 4.7 Hz), 126.0 (d, J_(C-P)=184 Hz),    127.4 (dq, J_(C-P, C-P)=6.1, 10.8 Hz), 134.3 (qd, J_(C-P, C-P)=32.4,    7.5 Hz), 138.6 (d, J_(C-P)=2.8 Hz), 142.1 (d, J_(C-P)=15.4 Hz); ¹¹B    NMR (130 MHz, CDCl₃) δ 30.8; ¹⁹F NMR (368 MHz, CDCl₃) δ −60.9 (s,    3F); ³¹P NMR (158 MHz, CDCl₃) δ 26.1; IR (KBr, ν/cm⁻¹) 2993, 1377,    1362,1325, 1308, 1280, 1244, 1148, 1135, 1104, 1059, 1029, 977, 964,    951, 849, 768, 682; HRMS (ESI⁺) Calcd for C₁₇H₂₅BF₃NaO₅P ([M+Na]⁺)    431.1382, Found 431.1379.

(6)N,N,N′,N′-Tetraethyl-P-(3-(4,4,5,5-tetramethyl-1,3,2dioxaborolan-2-yl)phenyl)phosphonicdiamide

-   296 yield; pale brown oil; ¹H NMR (500 MHz, CDCl₃) δ 1.04 (t, J=7.5    Hz, 12H), 1.33 (s, 12H), 3.00-3.13 (m, 8H), 7.35-7.47 (m, 1H), 7.84    (dd, J=11.5, 7.5 Hz, 1H), 7.88 (d, J=6.9 Hz, 1H), 8.19 (d, J=11.5    Hz, 1H); ¹³C NMR (125 MHz, CDCl₃) δ 13.6 (d, J_(C-P)=2.4 Hz), 24.9,    38.4 (d, J_(C-P)=4.8 Hz), 83.9, 127.5 (d, J_(C-P)=12.0 Hz), 132.4    (d, J_(C-P)=158 Hz), 134.5 (d, J_(C-P)=8.4 Hz), 137.2, 138.3 (d,    J_(C-P)=8.4 Hz); ¹¹B NMR (130 MHz, CDCl₃) δ 31.5; ³¹P NMR (158 MHz,    CDCl₃) δ 39.4; IR (neat, ν/cm⁻¹) 2973, 2932, 2871, 1594, 1470, 1383,    1357, 1317, 1262, 1216,1187, 1015, 945, 866, 841, 791, 739, 711,    671, 656; HRMS (ESI⁺) Calcd for C₂₀H₃₇BN₂O₃P ([M+H]⁺) 395.2635,    Found 395.2639.

N,N,N′,N′-Tetraethyl-P-(3,5-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)phosphonicdiamide

-   9% yield; pale brown solid; ¹H NMR (500 MHz, CDCl₃) δ 1.03 (t, J=6.9    Hz, 12H), 1.31 (s, 24H), 2.98-3.16 (m, 8H), 8.27 (d, J=12.1 Hz, 2H),    8.32 (s, 1H); ¹³C NMR (125 MHz, CDCl) δ 13.6 (d, J_(C-P)=2.4 Hz),    24.8, 38.3 (d, J_(C-P)=3.6 Hz), 83.8, 131.8 (d, J_(C-P)=154 Hz),    141.1 (d, J_(C-P)=9.6 Hz), 143.5 (d, J_(C-P)=2.4 Hz); ¹¹B NMR (130    MHz, CDCl3₃) δ 31.3; ³¹P NMR (158 MHz, CDCl₃) δ 39.5; IR (KBr,    ν/cm⁻¹) 2978, 2932, 2873, 1594, 1458, 1383, 1327,1313, 1272, 1220,    1189, 1163, 1144, 1020, 967, 945, 887, 847, 720, 659; HRMS    (ESI⁺)Calcd for C₂₆H₄₇B₂N₂NaO₅P ([M+Na]⁺) 543.3306, Found 543.3312.

(7)Dicyclohexyl(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)phosphineoxide

-   39% yield; pale brown solid; ¹H NMR (500 MHz, CDCl₃) δ 1.05-1.37 (m,    21H), 1.50-1.88 (m, 8H), 1.90-2.20 (m, 4H), 2.25-2.46 (m, 1H),    7.40-7.51 (m, 1H),7.68-7.83 (m, 1H), 7.93 (d, J=6.9 Hz, 1H),    7.98-8.07 (m, 1H); ¹³C NMR (125 MHz, CDCl₃) δ 24.6, 24.9, 25.5,    25.8, 26.2-26.5 (m, 2C), 35.2 (d, J_(C-P)=66.0 Hz), 84.0,    127.4-127.6 (m), 129.1 (d, J_(C-P)=85.2 Hz), 134.1-134.4 (m),    137.2-137.5 (m), 137.6; ¹¹B NMR (130 MHz, CDCl₃) δ 30.9; ³¹P NMR    (158 MHz, CDCl₃) δ 56.7; IR (KBr, ν/cm⁻¹) 2979, 2930, 2853, 1594,    1449, 1404, 1359, 1316, 1273, 1211, 1166, 1145, 1130, 1115, 1077,    963, 891, 853, 840, 759, 731, 709, 671; HRMS (ESI⁺) Calcd for    C₂₄H₃₈BNaO₃P ([M+Na]⁺) 439.2549, Found 439.2567.

Dicyclohexyl(3,5-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)phosphineoxide

-   35% yield; pale brown solid; ¹H NMR (500 MHz, CDCl₃) δ 1.08-1.36 (m,    33H), 1.51-1.86 (m, 8H), 1.94-2.13 (m, 4H), 2.23-2.45 (m, 1H), 8.11    (d, J=9.8 Hz, 1H), 8.37 (s, 1H); ¹³C NMR (125 MHz, CDCl₃) δ 24.7,    24.8, 25.5, 25.8, 26.2-26.5 (m, 2C), 35.3 (d, J_(C-P)=67.2 Hz),    84.0, 128.5 (d, J_(C-P)=85.2 Hz), 140.2 (d, J_(C-P)=7.2 Hz), 144.0;    ¹¹B NMR (130 MHz, CDCl₃) δ 31.2; ³¹P NMR (158 MHz, CDCl₃) δ 56.4; IR    (KBr, ν/cm⁻¹) 2977, 2929, 2853, 1594, 1449, 1383, 1329, 1272, 1215,    1176, 1143, 966, 888, 849, 716; HRMS (ESI⁺) Calcd for C₃₀H₅₀B₂O₅P    ([M+H]⁺) 543.3582, Found. 543.3588.

(8)Dicyclohexyl(2-methoxy-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)phosphineoxide

-   99% yield; pale yellow solid; ¹H NMR (400 MHz, CDCl₃) δ 1.14-1.19    (m, 4H), 1.21-1.42 (m, 16H), 1.44-1.51 (m, 4H), 1.64-1.68 (m, 4H),    1.80-1.84 (m, 2H), 2.03-2.17 (m, 4H), 3.86 (s, 3H), 6.87 (dd, J=8.7,    4.7 Hz, 1H), 7.91 (d, J=8.7 Hz, 1H), 8.36 (d, J=11.7 Hz, 1H); ¹³C    NMR (100 MHz, CDCl₃) δ 24.9, 25.7 (d, J_(C-P)=3.8 Hz), 25.9, 26.1    (d, J_(C-P)=3.8 Hz), 26.6 (d, J_(C-P)=12.3 Hz), 26.9 (d,    J_(C-P)=14.1 Hz), 36.9 (d, J_(C-P)=67.7 Hz), 55.1, 83.7, 109.3 (d,    J_(C-P)=6.9 Hz), 118.3 (d, J_(C-P)=83.8 Hz), 140.1 (d, J_(C-P)=1.9    Hz), 142.8 (d, J_(C-P)=3.8 Hz), 161.5 (d, J_(C-P)=5.6 Hz); ¹¹B NMR    (130 MHz, CDCl₃) δ 29.8; ³¹P NMR (158 MHz, CDCl₃) δ 59.5; IR (KBr,    ν/cm⁻¹) 2978, 2931, 2852, 1594, 1448, 1407, 1385, 1357, 1317, 1279,    1266, 1250, 1212, 1147, 1104, 1077, 1014, 964, 887, 851, 824, 750,    673; HRMS (ESI⁺) Calcd for C₂₅H₄₀BNaO₄P ([M+Na]⁺) 469.2655, Found    469.2668.

(9)Dicyclohexyl(2-chloro-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)phosphineoxide

-   99% yield; pale yellow solid; ¹H NMR (400 MHz, CDCl₃) δ 1.16-1.21    (m, 4H), 1.24-1.36 (m, 18H), 1.59-1.70 (m, 6H), 1.83-1.86 (m, 2H),    2.07-2.10 (m, 2H), 2.27-2.36 (m, 2H), 7.36 (dd, J=7.9, 3.6 Hz, 1H),    7.81 (d, J=7.9 Hz, 1H), 8.49 (d, J=10.5 Hz, 1H); ¹³C NMR (100 MHz,    CDCl₃) δ 24.9, 25.7 (d, J_(C-P)=1.4 Hz), 26.2 (d, J_(C-P)=3.3 Hz),    26.3 (d, J_(C-P)=3.8 Hz), 26.5 (d, J_(C-P)=12.7 Hz), 26.7 (d,    J_(C-P)=13.6 Hz), 37.4 (d, J_(C-P)=13.6 HZ), 84.2, 129.3 (d,    J_(C-P)=6.1 Hz), 130.1, 137.3 (d, J_(C-P)=6.1 HZ), 138.8 (d,    J_(C-P)=2.3 Hz), 143.1 (d, J_(C-P)=4.7 Hz); ¹¹B NMR (130 MHz, CDCl₃)    δ 30.5; ³¹P NMR (158 MHz, CDCl₃) δ 59.4; IR (KBr, ν/cm⁻¹) 2978,    2932, 2852, 1583, 1557, 1448, 1371, 1356, 1317, 1259, 1214, 1183,    1169, 1143, 1113, 1097, 1031, 964, 845, 755, 726, 671; HRMS (ESI⁺)    Calcd for C₂₄H₃₈BClO₃P ([14+H]⁺) 451.2340, Found 451.2341.

1. A bipyridyl compound represented by a general formula (1):

wherein A represents a single bond, a vinylene group or an ethynylenegroup; X represents an oxygen atom or a sulfur atom; n pieces of R¹ maybe the same or different, and R¹ represents a hydrogen atom, a halogenatom, an optionally substituted hydrocarbon group, an optionallysubstituted alkoxy group, an optionally substituted aryloxy group, anoptionally substituted amino group, a cyano group, a nitro group, or analkoxycarbonyl group, or two adjacent R¹ may form a saturated orunsaturated ring structure optionally containing a hetero atom togetherwith the carbon atoms bonded to the two R¹; R² represents a hydrogenatom, an optionally substituted hydrocarbon group, an optionallysubstituted alkoxy group, or an optionally substituted aryloxy group;and n represents a number of 1 to 4, wherein the optional substitutionon the hydrocarbon group of R¹ is 1 to 3 halogen atoms, a cyano group, anitro group, a halogeno C₁₋₆ alkyl group or a C₁₋₆ alkoxy group, whereinthe optional substitution on the alkoxy group and the aryloxy group ofR¹ is 1 to 3 halogen atoms, a cyano group, a nitro group, a halogenoC₁₋₆ alkyl group or a C₁₋₆ alkoxy group, wherein the optionalsubstitution on the amino group of R¹ is a C₁₋₆ alkyl group or ahalogeno C₁₋₆ alkyl group, wherein the optional substitution on thehydrocarbon group of R² is 1 to 3 halogen atoms, a cyano group, a nitrogroup, a halogeno C₁₋₆ alkyl group or a C₁₋₆ alkoxy group, wherein theoptional substitution on the alkoxy group and the aryloxy group of R² is1 to 3 halogen atoms, a cyano group, a nitro group, a halogeno C₁₋₆alkyl group or a C₁₋₆ alkoxy group.
 2. The bipyridyl compound accordingto claim 1, wherein A is a single bond.
 3. The bipyridyl compoundaccording to claim 1, wherein R¹ is a hydrogen atom, a halogen atom, analkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms, an arylgroup having 6 to 10 carbon atoms, an aryloxy group having 6 to 10carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a C₁-₆alkylamino group, a di (C₁₋₆ alkyl) amino group or a C₁-₁₀alkoxycarbonyl group.
 4. The bipyridyl compound according to claim 1,wherein R² is a hydrogen atom, an optionally substituted alkyl grouphaving 1 to 10 carbon atoms, an optionally substituted alkenyl grouphaving 2 to 10 carbon atoms, an optionally substituted cycloalkyl grouphaving 3 to 7 carbon atoms, an optionally substituted aryl group having6 to 10 carbon atoms, an optionally substituted alkoxy group having 1 to10 carbon atoms or an optionally substituted aryloxy group having 6 to10 carbon atoms.
 5. The bipyridyl compound according to claim 1, whereinwhen R² is a substituted non-heterocyclic group, the substitution isselected from the group consisting of 1 to 3 halogen atoms, a cyanogroup, a halogeno C₁₋₆ alkyl group and a C₁₋₆ alkoxy group.
 6. Thebipyridyl compound according to claim 1, which is1-(2-([2,2′-Bipyridin]-5-yl)phenyl)-3-(4-methoxyphenyl)urea.
 7. Thebipyridyl compound according to claim 1, which is1-(2-([2,2′-Bipyridin]-5-yl)phenyl)-3-cyclohexylthiourea.
 8. Thebipyridyl compound according to claim 1, which is1-(2-([2,2′-Bipyridin]-5-ylethynyl)phenyl)-3-phenylurea.